CN104592741B - High-performance environment-friendly single-component hydrophobic polyurethane grouting material and preparation method thereof - Google Patents
High-performance environment-friendly single-component hydrophobic polyurethane grouting material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-performance environment-friendly single-component hydrophobic polyurethane grouting material. The high-performance environment-friendly single-component hydrophobic polyurethane grouting material comprises the following substances: 100 parts of a polyurethane prepolymer, 1-10 parts of diatomaceous earth powder, 5-25 parts of polyurethane plasticizer, 5-25 parts of environment-friendly plasticizer, 10-35 parts of an environment-friendly solvent, 2-10 parts of a foam stabilizer, 0.2-2 parts of a catalyst and 0-0.2 part of a storage stabilizer. During construction, the hydrophobic polyurethane grouting material is single liquid grouting, the grouting material is environmentally friendly and free of pollution and can permeate inside various leakage water channels by virtue of grouting pressure and low viscosity, is in contact with water in the leakage gaps to rapidly absorb moisture by virtue of a porous filler and rapidly react with water for foaming. The grouting material and water are rapidly reacted and cured, the more excellent mechanical properties of the grouting material is ensured and the grouting material is high in dimensional stability so that the acid, salt alkali salt corrosion resistance of a product and engineering durability are increased to an utmost extent.
Description
Technical field
The invention belongs to be in the milk and water-proof plugging material field, more particularly to a kind of high-performance environment protection type one-component hydrophobicity
Polyurethane grouting material and preparation method thereof.
Background technology
Polyurethane grouting material is a kind of novel high polymer chemical grouting material, with permeability is good, water plugging effect is good, viscous
Various excellent properties such as knot power is strong, have been increasingly becoming one of chemical grouting material for being most widely used, are generally divided into hydrophilic
（Water solublity）And hydrophobicity（Oil-soluble）The concretion body strength of two big class, wherein hydrophobic polyurethane grouting material is big, impervious
By force, water reinforcement effect and project durability for waterborne polyurethane grouting material（Hydrophilic is easy to dehydration receipts
Contracting）More preferably.
However, the hydrophobic polyurethane grouting material main product for using at present also there are problems that, main performance
For：Though first, hydrophobicity slurry material meets water reaction rate within 300s, far below hydrophilic product（Tens seconds i.e. gel）,
The instant efficiency of water blockoff is significantly lower than the latter, while and because possess higher cost, have a strong impact on customer selecting such material
When confidence, cause so far domestic market hydrophilic still above oil-soluble；Second, the durability of polyurethane grouting material
Intensity and dried shrinkage factor depending on induration, although hydrophobicity slurry material will not be big after dehydration as hydrophilic slurry material
Inert organic solvents in volume contraction, but its system such as acetone, small molecule benzene-like compounds etc. can increase the drying of induration
Shrinkage factor, part producer with the addition of in the product substantial amounts of such diluent to pursue cost-effective, cause hydrophobicity to starch material
Equally exist the hidden danger that engineering is leaked again；Third, the acid and alkali-resistance salt corrosion of slurry material induration is not good enough, evil slightly geology ring is chronically at
Induration under border is easy to premature aging degraded, increases engineering and leaks probability again.
At home, currently for the exploitation of hydrophobic polyurethane grouting material, emphasis is concentrated on to be reduced and environmental protection to its cost
Property improve etc. aspect.Chinese patent CN102070761A, CN102093536A, CN103254403A are dredged with low molecular weight hydroxy-terminated
Aqueouss polyethers prepares plain edition one-component oil soluble polyurethane grouting material with polyisocyanates, has starched used in material small molecule benzene
The harmful organic solvent such as class and ketone, reduces product cost, but deteriorates the feature of environmental protection and durability of slurry material；In this regard, Chinese
Patent CN102492287A, CN102079862A, CN103030967A, CN103214823A use respectively different types of ether
The high boiling point such as class, esters environment-friendly type solvent is direct with plasticizer as diluent, has abandoned traditional effumability poisonous and harmful
Organic solvent, to improve the product feature of environmental protection, prepares environmentally friendly hydrophobic polyurethane grouting material.Above invention slurry material is in ring
Guarantor property improvement aspect has a certain upgrade, but key property the most key when actually used for slurry material-" with water reaction speed
Rate（Instantaneous water blockoff efficiency）" and " project durability（Long-term water blockoff efficiency）" lifting it is less, be directed under adverse circumstances significantly
The product for improving slurry material acid and alkali-resistance salt corrosion is not then more seen.
The content of the invention
The present invention is intended to provide a kind of high-performance environment protection type one-component hydrophobic polyurethane grouting material, by adding in system
Plus porous filler, hydrophobic property slurry material chance water water absorbing capacity, interface hydrophilic is poor because hydrophobicity is relatively strong to solve slurry material
Defect, by starch material molecular structure design with adjustment, ensure its mechanical property it is more excellent while so as to have
The excellent properties such as higher dimensional stability and splendid acid and alkali-resistance salt, the acidproof alkali salt that largely improve product is rotten
Corrosion and project durability.
The concrete technical scheme of the present invention is as follows：
A kind of high-performance environment protection type one-component hydrophobic polyurethane grouting material, in parts by weight including following material：
100 parts of base polyurethane prepolymer for use as
1 ~ 10 part of kieselguhr powder body
5 ~ 30 parts of polyurethane plasticizer
5 ~ 25 parts of environment-friendlyplasticizer plasticizer
10 ~ 35 parts of environment-friendly type solvent
2 ~ 10 parts of foam stabiliser
0.2 ~ 2 part of catalyst
0 ~ 0.2 part of storage stabilizing agent；
The base polyurethane prepolymer for use as is obtained by hydroxyl class compound and isocyanates reaction, and its isocyano-content is 20
~25%。
The isocyanates are preferably polyphenyl polymethylene polyisocyanates.
The hydroxyl class compound includes in parts by weight following material：100 parts of polymer polyatomic alcohol, poly- four is sub-
3 ~ 17 parts of ether glycol, 3 ~ 17 parts of end hydroxy butadiene, 3 ~ 17 parts of Based On Hydroxy-terminated Polyepichlorohydrin.Hydroxyl class compound
It is using the benefit of above-mentioned substance：Little in polyether segment polarity, ehter bond hydrolytic stability is good, and alkaline resistance properties is projected；Using certain
The aromatic polyester polyol or polycarbonate polyol of amount can improve the acid-proof alkaline of soft section；PPG segments hydrolytic resistance and
Oxidation resistent susceptibility is not so good as PTMG soft sections（Such as polytetramethylene ether diol）；Electron withdraw group is introduced in flexible polyurethane segment structure
（-Cl）, Based On Hydroxy-terminated Polyepichlorohydrin is such as used, the α hydrogen of ehter bond can be protected, improve the acid-proof alkaline of polyether structure.
The polymer polyatomic alcohol is polyether polyol or for polyether polyol is in mass ratio with PEPA
80:20~30:70 mix.
The polyether polyol is the dihydroxylic alcohols of molecular weight 400 ~ 2000 and/or the trihydroxylic alcohol of molecular weight 350 ~ 3000, gathers
Ethoxylated polyhydric alcohol is the copolymer obtained for initiator and propylene oxide open loop by low molecular weight polyols；
It is preferred described because aromatic polyester polyol or polycarbonate polyol can improve the acid-proof alkaline of soft section
One or more combination in any in the following material of PEPA：
1）Be polymerized the PEPA for obtaining by phthalic anhydride with dihydroxylic alcohols and/or trihydroxylic alcohol and/or binary acid, and molecular weight is
200 ~ 1200,300 ~ 400mgKOH/g of hydroxyl value；
2）Polycarbonate polyol, molecular weight is 1000 ~ 2000, and hydroxyl value is 50 ~ 120mgKOH/g；
3）By CO2The poly (propylene carbonate) polyhydric alcohol obtained with Polymerization of Propylene Oxide, molecular weight is 1800 ~ 2700, hydroxyl value
For 40 ~ 55mgKOH/g.
The end hydroxy butadiene is selected from the Polybd R-15M of Sinclair companies of Britain, Japanese Cao and reaches（Strain）'s
Nisso PB, the Polybd R-45HT of ARCO companies of Japan, the Polybd R-CS15 of ARCO companies of Japan, ARCO companies of Japan
Polybd R-CN15 in one kind.
In order that the degree of cross linking provided after viscosity, molecular weight and crosslinking is moderate, the preferred terminal hydroxy group polycyclic oxygen chlorine
Propane is by the ethers oligomer that dihydroxylic alcohols or trihydroxylic alcohol are initiator, epoxychloropropane cation ring-opening polymerization, sense
Spend for 1.8 ~ 2, molecular weight is 2800 ~ 3000.
In order that the degree of cross linking provided after viscosity, molecular weight and crosslinking is moderate, preferred of the present invention poly- four is sub-
Ether glycol molecular weight is preferably 650 ~ 2000.
Kieselguhr powder body of the present invention is porous filler, and its granularity is preferably 300 ~ 2000 mesh；So that porous
The performance of filler is more excellent, dispersibility number.
The polyurethane plasticizer is the polyether polyol and oligomeric isocyanates of monohydroxy compound end-blocking, above-mentioned poly-
Carry out of the preparation method of urethane plasticizer in Chinese patent CN101805588A：Polyether polyol is added into reactor
In, vacuum -0.08 ~ -0.1MPa, it is dehydrated 2 hours at 110 ~ 120 DEG C, 60 ~ 65 DEG C are then cooled to, add aliphatic isocyanide
Acid esters and/or alicyclic isocyanate, are warming up to 75 ~ 80 DEG C of 2 ~ 4h of reaction, add monohydroxy compound, continue to react 2h,
Cooling discharge, obtains liquid polyurethane plasticizer.Wherein, the polyether polyol in described polyurethane plasticizer selected from N204,
One kind in N210, N220；Aliphatic isocyanates and/or alicyclic isocyanate in described polyurethane plasticizer are selected from
Hexamethylene diisocyanate, isophorone diisocyanate, hexa-methylene -1,6- diisocyanate, hydrogenation phenylmethane two are different
One kind in cyanate；Monohydroxy compound in the polyurethane plasticizer is the alcohol of single functionality, selected from n-butyl alcohol, positive penta
One kind of alcohol, hexanol.Isocyano and polyether polyol contained by the aliphatic isocyanates and/or alicyclic isocyanate
Mol ratio between middle institute's hydroxyl is 2 ~ 2.15:1, in the performed polymer after the completion of above-mentioned reaction remain isocyano with it is described
Mol ratio in monohydroxy compound between institute's hydroxyl is 1:0.95~1.
The present invention using said method be obtained polyurethane plasticizer benefit be：Raw material is easy to get, preparation process is simple, synthesis
Molecular weight of product, modest viscosity, plasticization effect is good.
The environment-friendlyplasticizer plasticizer is that the synthesis vegetable esters or composite plant ester being composited are extracted from various plants oil；
Preferably Suzhou Yi Gete Chemical Co., Ltd.s product diethylene glycol dibenzoate（DEDB）.
It is low toxicity or non-toxic type high boiling solvent, preferably Allyl carbonate, mixing binary that the environment-friendly type solvent is actual
Acid esters（DBE）In the mixing of one or two arbitrary proportions.
The foam stabiliser is Siloxane-Oxyalkylene Copolymers, Tween-60, tween 80；Wherein, it is described polyether-modified poly-
Siloxanes is polyethers and polydimethylsiloxane（Polyethers is 0.01 ~ 0.2 with the mass ratio of both polydimethylsiloxane）Grafting
A kind of organosilicon nonionic surfactant of copolymerization.
The catalyst is amines catalyst and organometallic catalysts are 1 in mass ratio:0.05 ~ 0.15 formed answer
Compound；Wherein, the amines catalyst is selected from five methyl diethylentriamine, double（Dimethylaminoethyl）The double morpholines of ether, 2,2-
Base Anaesthetie Ether, N, N- dimethyl benzylamines, triethylene diamine, N, the one kind in N- dimethyl cyclohexyl amines；The organic metal class
The one kind of catalyst in stannous octoate, dibutyl tin laurate, isooctyl acid potassium.Using amines catalyst and organic metal
Class catalyst is used in conjunction with, concerted catalysis speed faster, it is less using tin catalyst abscess-size, it is solid using amine catalyst foam
Knot body is more stable.
The storage stabilizing agent is selected from anhydrous phosphoric acid, tartaric acid, Benzenecarbonyl chloride., triphenyl phosphate, triphenyl phosphite, carbon
One kind in sour tetra-ethyl ester, tetraethyl orthosilicate.
The invention further relates to the preparation method of above-mentioned high-performance environment protection type one-component hydrophobic polyurethane grouting material, its feature
It is to comprise the steps：
（1）The preparation of base polyurethane prepolymer for use as
By polymer polyatomic alcohol, polytetramethylene ether diol, Based On Hydroxy-terminated Polyepichlorohydrin, end hydroxy butadiene together
In adding reactor, vacuum -0.08 ~ -0.1MPa, at 110 ~ 120 DEG C after dehydration 2 ~ 3 hours, 55 ~ 65 DEG C are cooled to, lead to nitrogen
Gas or dry air release vacuum；Polyisocyanates is added, in a nitrogen atmosphere after 30 ~ 60min of insulated and stirred, it is warming up to 70 ~
80 DEG C, react 2 ~ 3 hours, 50 ~ 60 DEG C are cooled to after the completion of reaction, obtain base polyurethane prepolymer for use as；
（2）The preparation of polyurethane grouting material
Polyurethane plasticizer, kieselguhr powder body, environment-friendly type solvent, environment-friendly type plasticising are added in above-mentioned base polyurethane prepolymer for use as
Agent, foam stabiliser, catalyst and storage stabilizing agent, obtain polyurethane grouting material after stirring.
The polyurethane grouting material of the present invention in preparation process each raw material by strict processed and aqueous
Rate is checked, and after the material fill of obtained slurry nitrogen encapsulation process is led to.
It is single liquid grouting when the high-performance environment protection type one-component hydrophobic polyurethane grouting material of the present invention is constructed, slurry material environmental protection
It is pollution-free, grouting pressure and the low viscosity of itself can be relied on to penetrate in all kinds of seepage aquaporins, meet after water in seepage crack
Itself porous filler rapid adsorption moisture can be relied on and foaming, chance water is reacted rapidly with water and be swift in response, ensured after solidification
Dimensional stability is high while slurry material mechanical property is more excellent, largely improve product acid and alkali-resistance salt corrosion and
Project durability.Can effectively realize concrete works under various adverse circumstances, hydraulic engineering, reservoir dam, bridge foundation,
The impervious leakage-stopping and reinforcing of the crack of the buildings such as civilian installation, expansion joint, construction joint, structural joint and mine retaining wall.
Specific embodiment
The concrete application example of the present invention is the following is, but the present invention does not receive following examples content constraints；In the present invention
Raw material is commercially available with reagent.
Embodiment 1
90.4g hexa-methylene -1,6- diisocyanate is added to be warming up to 75 DEG C of reactions 100g polyether polyol N204
3h, adds 40.5g n-butyl alcohol, continues to react 2h, and cooling discharge obtains liquid polyurethane plasticizer.
12g polyether polyol N210 is weighed, 5g polyether polyol N220,10g PEPA PS-3152,3g polyethers is more
First alcohol 303,1g polytetramethylene ether diols 1000,1g end hydroxy butadiene Polybd R-15M（Molecular weight 2500 ~ 2800,
44 ~ 58mgKOH/g of hydroxyl value,）, 5g Based On Hydroxy-terminated Polyepichlorohydrins（Molecular weight 2800 ~ 3000,33 ~ 40mgKOH/g of hydroxyl value, sense
Spend for 1.8 ~ 2）Add together in reactor, vacuum -0.08 ~ -0.1MPa, at 110 ~ 120 DEG C after vacuum dehydration 2h（Former material
Material moisture content≤0.05%）55 DEG C are cooled to, 113g polyphenyl polymethylene polyisocyanates are added in reactor（- NCO contains
Amount 30.5 ~ 32%）, in a nitrogen atmosphere after insulated and stirred 30min, 70 DEG C are warming up to, react 3 hours, temperature drop after the completion of reaction
To 50 DEG C, base polyurethane prepolymer for use as is obtained；7.5g liquid polyurethane plasticizers, 15g diatoms are added in above-mentioned base polyurethane prepolymer for use as
Native powder body（300 mesh）, 30g Allyl carbonaties, 37.5g synthesis vegetable esters DEDB, 6g polyether modified silicon oils, 0.19g tin dilaurates
Dibutyl tin and 1.3g dual-morpholinyl diethyl ethers（DMDEE）, grouting material is obtained after stirring.
The important technological parameters of 1 embodiment of table 1
Embodiment 2
100g polyether polyol N210 is added in reaction vessel, -0.08 ~ -0.1MPa, vacuum dehydration 2 at 110 ~ 120 DEG C
Hour, 60 ~ 65 DEG C are cooled to, add 33.6g1, hexamethylene-diisocyanate to be warming up to 80 DEG C of reaction 2h, add the positive fourths of 14.4g
Alcohol, continues to react 2h, and cooling discharge obtains liquid polyurethane plasticizer；
Weigh 20g polyether polyol N204,10g polyether polyol 303,5g PTMEG1800,1g end hydroxy butadienes
Polybd R-45HT（Molecular weight 2700 ~ 2900,42 ~ 50mgKOH/g of hydroxyl value,）, 1g Based On Hydroxy-terminated Polyepichlorohydrins（Molecular weight
2800 ~ 3000,33 ~ 40mgKOH/g of hydroxyl value, degree of functionality is 1.8 ~ 2）, add together in reaction vessel, vacuum dehydration 2h, dehydration
Afterwards（Raw material moisture content≤0.05%）55 ~ 80 DEG C are cooled to, 143g PAPI are added in reaction vessel, protected in a nitrogen atmosphere
After temperature stirring 30min, 70 DEG C are warming up to, are reacted 3 hours, temperature is down to 50 DEG C after the completion of reaction, obtains base polyurethane prepolymer for use as；To
45g liquid polyurethane plasticizers, 1.8g kieselguhr powder body are added in above-mentioned performed polymer（2000 mesh）, 40g Allyl carbonaties, 23g
Mixed dibasic acid ester DBE, 9g synthesize vegetable esters or composite plant ester, 18g polyether modified silicon oils, the double morpholinyl diethyl of 0.34g
Ether, 0.02g dibutyl tin laurates, 0.09g anhydrous phosphoric acids discharge after stirring.
The important technological parameters of 2 embodiment of table 2
Embodiment 3
100g polyether polyol N220 is added in reactor, vacuum -0.08 ~ -0.1MPa, 2 is dehydrated at 110 ~ 120 DEG C
Hour, 60 DEG C are cooled to, add 16.8g hexa-methylene -1,6- diisocyanate to be warming up to 80 DEG C of reaction 2h, adding 10g just
Hexanol, continues to react 2h, and cooling discharge obtains liquid polyurethane plasticizer；
Weigh 12g polyether polyol N204,5g polyether polyol N220,10g poly (propylene carbonate) polyhydric alcohol（Molecular weight
1800 ~ 2200,45 ~ 55mgKOH/g of hydroxyl value）, 3g polyether polyol 303,1.1g PTMEG650,5g end hydroxy butadienes
Polybd CS-15（Molecular weight 2800 ~ 3600,34 ~ 48mgKOH/g of hydroxyl value）, 1g Based On Hydroxy-terminated Polyepichlorohydrins（Molecular weight
2800 ~ 3000,33 ~ 40mgKOH/g of hydroxyl value）, add together in reaction vessel, vacuum dehydration 2h, after dehydration（Raw material moisture content
≤0.05%）55 ~ 80 DEG C are cooled to, 250gPAPI is added in reactor, in a nitrogen atmosphere after insulated and stirred 30min, heated up
To 80 DEG C, react 2 hours, temperature is down to 50 DEG C after the completion of reaction, obtains base polyurethane prepolymer for use as；Add in above-mentioned performed polymer
43g liquid polyurethane plasticizers, 14g kieselguhr powder body（600 mesh）, 28.7g thricarbonate propylenes, 57.4g synthesis vegetable esters
DEDB, 5.74g polyether modified silicon oil, 5.3g dual-morpholinyl diethyl ethers（DMDEE）, 0.4g stannous octoates, the anhydrous phosphorus of 0.57g
Acid, discharges after stirring.
The important technological parameters of 3 embodiment of table 3
Embodiment 4
100g polyether polyol N210 is added in reactor, vacuum -0.08 ~ -0.1MPa, 2 is dehydrated at 110 ~ 120 DEG C
Hour, 60 ~ 65 DEG C are cooled to, add 33.6g hexa-methylene -1,6- diisocyanate to be warming up to 80 DEG C of reaction 2h, add
20g hexanol, continues to react 2h, and cooling discharge obtains liquid polyurethane plasticizer；
Weigh 15g polyether polyol N204,10g polycarbonate polyols（Molecular weight 1000, hydroxyl value 112.2mgKOH/g）,
3g polyether polyol 3050,2g polyether polyol N330,2g PTMEG2000,3g end hydroxy butadiene Polybd CN-15
（Molecular weight 3300 ~ 4400,28 ~ 40mgKOH/g of hydroxyl value）, 2g Based On Hydroxy-terminated Polyepichlorohydrins（Molecular weight 2800 ~ 3000, hydroxyl value
33 ~ 40mgKOH/g, degree of functionality is 1.8 ~ 2）, add together in reaction vessel, after vacuum dehydration 2h（Raw material moisture content≤
0.05%）, 60 DEG C are cooled to, 153g polyisocyanates is added in reactor, in a nitrogen atmosphere after insulated and stirred 30min, rise
Temperature is reacted 3 hours to 70 DEG C, and temperature is down to 50 DEG C after the completion of reaction, obtains base polyurethane prepolymer for use as；Add in above-mentioned performed polymer
47.5g liquid polyurethane plasticizers, 6g kieselguhr powder body（800 mesh）, 37g diethylene glycol dimethyl ethers, 38g synthesis vegetable esters
DEDB, 6.5g tween 80,2.2 and 0.2g triethylamines, 0.15g tartaric acid obtains grouting material after stirring.
The important technological parameters of 4 embodiment of table 4
Embodiment 5
Polyether polyol 100gN210 is added in reaction vessel, -0.08 ~ -0.1MPa, vacuum dehydration 2 at 110 ~ 120 DEG C
Hour, 60 ~ 65 DEG C are cooled to, add 33.6g1, hexamethylene-diisocyanate to be warming up to 80 DEG C of reaction 2h, add the positive fourths of 14.8g
Alcohol, continues to react 2h, and cooling discharge obtains liquid polyurethane plasticizer；
Weigh 17g polyether polyol N204,5g polycarbonate polyols（Molecular weight 1000, hydroxyl value 112.2mgKOH/g）,
5g poly (propylene carbonate) polyhydric alcohol（Molecular weight 2300 ~ 2700,40 ~ 50mgKOH/g of hydroxyl value）, 3g polyether polyol N303,
3gPTMEG650,2g end hydroxy butadiene Nisso PB（Molecular weight 2000, hydroxyl value 56mgKOH/g）, 2g terminal hydroxy group polycyclic oxygen
Chloropropane（Molecular weight 2800 ~ 3000,33 ~ 40mgKOH/g of hydroxyl value, degree of functionality is 1.8 ~ 2）, add together in reaction vessel, very
After sky dehydration 2h（Raw material moisture content≤0.05%）, 60 DEG C are cooled to, 120gPAPI is added in reactor, in nitrogen atmosphere
After lower insulated and stirred 30min, 70 DEG C are warming up to, are reacted 3 hours, temperature is down to 50 after the completion of reactionOC, obtains polyurethane prepolymer
Body；31g liquid polyurethane plasticizers, 5g kieselguhr powder body are added in above-mentioned performed polymer（800 mesh）, 20g diethylene glycol diethyls
Ether, 30g synthesis vegetable esters DEDB, 5g polyether modified silicon oils, 1.72 dual-morpholinyl diethyl ethers（DMDEE）With 0.15g T12,
0.08g anhydrous phosphoric acids, obtain grouting material after stirring.
The important technological parameters of 5 embodiment of table 5
Embodiment 6
Polyether polyol 100gN220 is added in reactor, vacuum -0.08 ~ -0.1MPa, 2 is dehydrated at 110 ~ 120 DEG C
Hour, 60 DEG C are cooled to, add 16.8g hexa-methylene -1,6- diisocyanate to be warming up to 80 DEG C of reaction 2h, adding 10g just
Hexanol, continues to react 2h, and cooling discharge obtains liquid polyurethane plasticizer；
Weigh 9g polyether polyol N210,11g aromatic polyester polyol RAYNOL PS-400A, 10g polymerized thylene carbonates third
Ester polyol（Molecular weight 1800 ~ 2200,45 ~ 55mgKOH/g of hydroxyl value）, 3gPTMEG2000,2g end hydroxy butadiene Polybd
R-15M（Molecular weight 2500 ~ 2800,44 ~ 58mgKOH/g of hydroxyl value）, 2g Based On Hydroxy-terminated Polyepichlorohydrins（Molecular weight 2800 ~ 3000,
33 ~ 40mgKOH/g of hydroxyl value, degree of functionality is 1.8 ~ 2）, add together in reaction vessel, after vacuum dehydration 2h（Raw material moisture content
≤0.05%）, 60 DEG C are cooled to, 140gPAPI is added in reactor, in a nitrogen atmosphere after insulated and stirred 30min, it is warming up to
70 DEG C, react 3 hours, temperature is down to 50 DEG C after the completion of reaction, obtains base polyurethane prepolymer for use as；44g is added in above-mentioned performed polymer
Liquid polyurethane plasticizer, 6g kieselguhr powder body（2000 mesh）, 35g mixes dicarboxylic acid dimethyl ester, 35g synthesis vegetable esters DEDB, 6g
Polyether modified silicon oil, 2g dual-morpholinyl diethyl ethers（DMDEE）With 0.17g triethylamines, 0.09g tartaric acid, obtain after stirring
To grouting material.
The important technological parameters of 6 embodiment of table 6
Comparative example：The technical specification of oil soluble polyurethane grouting material is such as described in the embodiment one in CN102079862A
Shown in table 7, polyurethane grouting material of the present invention has more advantage in terms of acid and alkali-resistance salt corrosion and durability.
Table 7
Claims (8)
1. a kind of high-performance environment protection type one-component hydrophobic polyurethane grouting material, it is characterised in that include in parts by weight as
Lower material：
The base polyurethane prepolymer for use as by hydroxyl class compound and isocyanates reaction be obtained, its isocyano-content be 20～
25%；
The hydroxyl class compound includes in parts by weight following material：100 parts of polymer polyatomic alcohol, polytetramethylene
3～17 parts of ether glycol, 3～17 parts of end hydroxy butadiene, 3～17 parts of Based On Hydroxy-terminated Polyepichlorohydrin；
The polymer polyatomic alcohol is polyether polyol or is in mass ratio 80 for polyether polyol and PEPA:20
～30:70 mix.
2. high-performance environment protection type one-component hydrophobic polyurethane grouting material according to claim 1, it is characterised in that described
Polyether polyol is the dihydroxylic alcohols of molecular weight 400～2000 and/or the trihydroxylic alcohol of molecular weight 350～3000, and polyether polyol is
It is the copolymer that initiator and propylene oxide open loop are obtained by low molecular weight polyols；
One or more combination in any of described PEPA in following material：
1) be polymerized the PEPA for obtaining by phthalic anhydride with dihydroxylic alcohols and/or trihydroxylic alcohol and/or binary acid, molecular weight be 200～
1200,300～400mgKOH/g of hydroxyl value；
2) polycarbonate polyol, molecular weight is 1000～2000, and hydroxyl value is 50～120mgKOH/g；
3) by CO2The poly (propylene carbonate) polyhydric alcohol obtained with Polymerization of Propylene Oxide, molecular weight is 1800～2700, and hydroxyl value is 40
～55mgKOH/g.
3. high-performance environment protection type one-component hydrophobic polyurethane grouting material according to claim 1, it is characterised in that described
End hydroxy butadiene is selected from Nisso PB, the Japan that the Polybd R-15M of Sinclair companies of Britain, Japanese Cao reach (strain)
The Polybd R-45HT of ARCO companies, the Polybd R-CS15 of ARCO companies of Japan, the Polybd R- of ARCO companies of Japan
One kind in CN15.
4. high-performance environment protection type one-component hydrophobic polyurethane grouting material according to claim 1, it is characterised in that described
Based On Hydroxy-terminated Polyepichlorohydrin is by the ether that dihydroxylic alcohols or trihydroxylic alcohol are initiator, epoxychloropropane cation ring-opening polymerization
Quasi-oligomer, degree of functionality is 1.8～2, and molecular weight is 2800～3000.
5. high-performance environment protection type one-component hydrophobic polyurethane grouting material according to claim 1, it is characterised in that described
Polyurethane plasticizer is the polyether polyol and oligomeric isocyanates of monohydroxy compound end-blocking.
6. high-performance environment protection type one-component hydrophobic polyurethane grouting material according to claim 1, it is characterised in that described
Environment-friendlyplasticizer plasticizer is that the synthesis vegetable esters or composite plant ester being composited are extracted from various plants oil.
7. high-performance environment protection type one-component hydrophobic polyurethane grouting material according to claim 1, it is characterised in that described
One or two arbitrary proportion mixing of environment-friendly type solvent in Allyl carbonate, mixed dibasic acid ester (DBE)；
The foam stabiliser is Siloxane-Oxyalkylene Copolymers, Tween-60 or tween 80；
The catalyst is amines catalyst and organometallic catalysts are 1 in mass ratio:0.05～0.15 formed it is compound
Thing；
The storage stabilizing agent is selected from anhydrous phosphoric acid, tartaric acid, Benzenecarbonyl chloride., triphenyl phosphate, triphenyl phosphite, carbonic acid four
One kind in ethyl ester, tetraethyl orthosilicate.
8. the preparation method of the high-performance environment protection type one-component hydrophobic polyurethane grouting material described in any one of claim 1 to 7,
It is characterized in that comprising the steps：
1) preparation of base polyurethane prepolymer for use as
Polymer polyatomic alcohol, polytetramethylene ether diol, Based On Hydroxy-terminated Polyepichlorohydrin, end hydroxy butadiene are added together
In reactor, vacuum -0.08～-0.1MPa, at 110～120 DEG C after dehydration 2～3 hours, 55～65 DEG C are cooled to, lead to nitrogen
Gas or dry air release vacuum；Polyisocyanates is added, in a nitrogen atmosphere after 30～60min of insulated and stirred, 70 is warming up to
～80 DEG C, react 2～3 hours, 50～60 DEG C are cooled to after the completion of reaction, obtain base polyurethane prepolymer for use as；
2) preparation of polyurethane grouting material
To in above-mentioned base polyurethane prepolymer for use as add polyurethane plasticizer, kieselguhr powder body, environment-friendly type solvent, environment-friendlyplasticizer plasticizer,
Foam stabiliser, catalyst and storage stabilizing agent, obtain polyurethane grouting material after stirring.
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| WO2017017089A1 (en) * | 2015-07-30 | 2017-02-02 | Sika Technology Ag | Hydrophobic and highly elastic two-component polyurethane composition having mechanical properties and adhesive properties not dependent on temperature |
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