CN103626951A - Special engineering material for reinforcement and preparing method therefor - Google Patents
Special engineering material for reinforcement and preparing method therefor Download PDFInfo
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- CN103626951A CN103626951A CN201210297269.1A CN201210297269A CN103626951A CN 103626951 A CN103626951 A CN 103626951A CN 201210297269 A CN201210297269 A CN 201210297269A CN 103626951 A CN103626951 A CN 103626951A
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
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- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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Abstract
The invention relates to a special engineering material for reinforcement and a preparing method therefor. The special engineering material for reinforcement is composed of a component A and a component B, and the volume ratio between the component A and the component B ranges from 1:4 to 4:1. The component A comprises, by weight, 30-80 parts of polyether polyol, 5-25 parts of polyester polyol, 1-20 parts of a chain extender, 5-20 parts of a fire retardant, 5-10 parts of a plasticizer, and 0.2-6 parts of a catalyst. The component B comprises isocyanate and/or a modified derivative of the isocyanate. Compared with a conventional material, the special engineering material for reinforcement has greatly reduced cost, has greatly reduced reaction temperature, and is of improved flame resistance, and a polyurethane consolidating product obtained after a mixing reaction is characterized by super-high mechanical properties, low deformation, high bearing strength and high tensile strength. The deformation is within 10%, the bearing strength can reach more than 70 MPa, and the tensile strength is greater than 16 MPa.
Description
Technical field
The present invention relates to a kind of special engineered material and preparation method thereof for reinforcing, more specifically, relate to a kind of urethane reinforcing engineering materials.
Background technology
At present, the major Safety of puzzlement Safety of Coal Mine Production is the natural disasteies such as wall caving, inbreak of the down-hole geologic medias such as tunnel.There is inefficiency, time-consuming in tradition reinforcement technique.Make the underground workss such as colliery have great technical difficulty in the problems such as processing wall caving inbreak.
Polyurethanes novel high polymer injecting paste material, there is modest viscosity, time of coagulation is adjustable, the advantages such as fixed rear quality is light, thermal conductivity is low, resistance to chemical attack, can fundamentally address the above problem, and in a lot of big-and-middle-sized collieries, have obtained promotion and application widely.
As reinforcing polyurethane material, several materials is disclosed in prior art.For example CN102532455A discloses a kind of polyurethane polymer material for coal rock mass reinforcement, it is comprised of A component and B component, wherein: A component is according to parts by weight meter: polyether glycol A:70～85 part, polyether glycol B:10～25 part, polyester polyol C:0～5 part, polar solvent: 3～7 parts, catalyzer: 0.2～2.0 part, fire retardant: 20～30 parts; B component is polyphenyl polymethylene polyisocyanates.
CN102558498A discloses a kind of coal mine polyurethane and has reinforced and compaction material, by separately independently A component and B component form, and the mass ratio of A component and B component is 1～2: 1, described A component is polymethylene multi-phenenyl isocyanate; Described B component is mixed by polyether glycol 33～70wt%, polyester polyol 0～40wt%, composite catalyst 0.1～1.5wt%, composite flame-retardant agent 6～30wt%, whipping agent 0～15wt%, stablizer 0.5～2.5wt%, suds-stabilizing agent 0.5～10wt%, static inhibitor 0.1～5wt%, softening agent 5～25wt%, at 30～50 ℃ of stirring reactions, within 0.5～2 hour, obtains.
But there is the problems such as temperature of reaction is higher, cost is higher in the urethane reinforcement material of prior art.
The inventor be take down-hole particular surroundings as major consideration, good in conjunction with polyurethane material viscosity low-permeability, react quick efficiency higher, reinforce after moulding the peculiar advantages such as induration mechanical strength is high, environment friendly and pollution-free with coal and rock, developed mechanical property excellent equally, but the slip casting strengthening material of new generation that price significantly reduces, temperature of reaction reduces greatly, flame retardant resistance improves.The present invention is intended to solve the problems such as wall caving inbreak of puzzlement underground construction, the complex geological conditions such as fractured coal and rock zone of fold is carried out to the processing of quickness and high efficiency, for the efficient production and construction of downhole safety provides powerful guarantee.
In order to solve the problems such as wall caving inbreak of puzzlement underground construction, the complex geological conditions such as fractured coal and rock zone of fold are carried out to the processing of quickness and high efficiency, for the efficient production and construction of downhole safety provides powerful guarantee, the inventor is through further investigation, a kind of cheapness, temperature of reaction is low, mechanical property is high, flame retardant resistance the is high special engineered material of reinforcing are provided, and it is a kind of polyurethane material.
Summary of the invention
One object of the present invention is to provide a kind of reinforcing special engineered material, A component and B component, consists of, and the volume ratio of described A component and B component is 1: 4～4: 1; Wherein said A component comprises polyether glycol 30-80 mass parts, polyester polyol 5-25 mass parts, chainextender 1-20 mass parts, fire retardant 5-20 mass parts, softening agent 5-10 mass parts, catalyzer 0.2-6 mass parts; Described B component is isocyanic ester and/or its modification derivant.
Another object of the present invention is to provide the preparation method who reinforces with special engineered material, wherein, each material waterproof of A component is mixed to prepare A component, during use, A component and B component are waited to solidify according to volume ratio mixing injection coal (rock) layer of 1: 4～4: 1.
Below respectively each constitute of A component and B component is described in detail.
Component A
1. polyether glycol
Polyether glycol is the oligopolymer of terminal hydroxy group, and the hydroxyl on main chain has ehter bond to connect, and is to take low molecular weight polyols, polyamine or be initiator containing the compound of reactive hydrogen, forms with olefin oxide ring-opening polymerization under catalyst action.The present invention's polyether glycol used is one or more in polyoxypropyleneglycol, polyoxytrimethylene triol, TriMethylolPropane(TMP) polyethers and polytetrahydrofuran diol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol.
The kind of conventional polyether glycol has following several:
Polyoxypropyleneglycol
Polyoxypropyleneglycol claims again polypropylene glycol (polyoxypropylene glycol is called for short PPG), and its preparation completes in glass inner-lining or stainless steel cauldron.By initiator (1,2-propylene glycol or dipropylene glycol) and the mixture of catalyzer (potassium hydroxide) add in the still of Kaolinite Preparation of Catalyst, be heated to 80～100 ℃, under vacuum, remove the solvent in catalyzer, to impel the generation of alcoholate.Then catalyzer is proceeded in reactor, be heated to 90～120 ℃, at this temperature, propylene oxide is added in still, make still internal pressure keep 0.07～0.35MPa.Under this temperature and pressure, propylene oxide carries out successive polymerization, until arrive at certain molecular weight.Under negative depressed state, steam after remaining propylene oxide monomer, during polyether mixture is proceeded to and still, with acidic substance, neutralize, then after filtration, refine, add stablizer to obtain product.
Polytetrahydrofuran diol
Polytetrahydrofuran diol (polytetrahydrofuran glycol, be called for short PTHF) or polyoxy tetramethylene glycol (polyoxytetramethylene glycol is called for short PIG, PTMEG, PTMG, PTMO) by tetrahydrofuran (THF) ring-opening polymerization under cationic catalyst exists, made.Production technique: add tetrahydrofuran (THF) in reactor, temperature drops to below-5 ℃, under violent stirring, drip oleum catalyzer, keep reaction mass low temperature, under stirring, add quantitative water, be warming up to 70～90 ℃, steam unreacted tetrahydrofuran monomers, through stratification, neutralization, filter, vacuumize etc. after operation, make polytetrahydrofuran diol.
Polytetrahydrofuran diol price is higher, is generally used for the high performance polyurethane material of preparation, and its goods have the performances such as outstanding low temperature resistant, water-fast, oil resistant, wear-resisting and resistance to mould.
Tetrahydrofuran (THF)-propylene oxide copolymerization glycol
Tetrahydrofuran (THF)-propylene oxide copolymerization glycol (tetrahydrofuranoxide propylene copolymer glycol) is ring-opening polymerization under the katalysis of lewis acid by tetrahydrofuran (THF) and propylene oxide, through operations such as neutralization, washing, dehydration and filtrations, makes.Structural formula is as follows:
The product specification of tetrahydrofuran (THF)-propylene oxide copolymerization glycol is in Table 3-28.This copolyether cost is more cheap than pure polytetrahydrofuran diol, and its product properties is similar to PTMG, is specially adapted to manufacture low temperature resistant polyurethane material (resist cold and can reach-200 ℃).
The present invention's polyether glycol used is preferably molecular weight and is respectively 200-3000 (preferably 800-2000), hydroxyl value 50～700mKOH/g.Acid number≤0.15mKOH/g, the polyether glycol of viscosity 50～800mPas.If the molecular weight of polyether glycol is less than 200, just there is no all characteristics of macromolecule polyether glycol, if molecular weight is too large, corresponding viscosity is just too large, to construction, makes troubles; Hydroxyl value is less than at 50 o'clock, just there is no the effective radical reaction in enough hydroxyls and B material in polyether glycol, reinforces little by the ultimate compression strength of special engineered material, if hydroxyl value is greater than at 700 o'clock, due to the hydrogen bond action between hydroxyl, make polyether glycol obtain viscosity and increase, to construction, make troubles; The viscosity of response is little, must be that molecular weight is little and hydroxyl value is low, be that product is not up to standard, otherwise viscosity is large, to construction, makes troubles.
In A component, the content of polyether glycol is 30 quality %-80 quality %, is preferably 35 quality %-70 quality %, more preferably 50 quality %-60 quality %.If the content of polyether glycol is lower than 30 quality %, the hydroxyl in A component does not reach requirement.If higher than 80 quality %, the hydroxyl in A component has residue, causes wastage of material phenomenon
2. polyester polyol
Polyester polyol viscosity of the present invention is 50～800mPas, hydroxyl value 30～600mKOH/g, acid number≤0.15mKOH/g, moisture < 0.1%.Preferably, polyester polyol of the present invention is selected from polyethylene glycol adipate glycol, poly-adipate glycol propylene glycol ester glycol, poly-hexanodioic acid glycol ether esterdiol, poly-adipate glycol glycol ether esterdiol, poly-hexanodioic acid-1,4-butanediol ester glycol, poly-adipate glycol-1,4-butanediol ester glycol, poly-hexanodioic acid neopentyl glycol-1,6-hexylene glycol esterdiol, poly-hexanodioic acid Viscotrol C ester polyol, poly--6-caprolactone glycol, poly-carbonic acid 1, one or more in the own-ol esterdiol of 6-etc.Preferred polyethylene glycol adipate glycol, poly-adipate glycol propylene glycol ester glycol, poly-hexanodioic acid glycol ether esterdiol, poly-adipate glycol glycol ether esterdiol, poly-hexanodioic acid-BDO esterdiol.Polyethylene glycol adipate glycol most preferably.
In A component, the content of polyether glycol is 5 quality %-25 quality %, is preferably 8 quality %-20 quality %, more preferably 10 quality %-18 quality %.If, lower than 5 quality %, having, the content of polyether glycol do not improve the close-burning effect of product.If higher than 18 quality %, product ultimate compression strength declines.
3. chainextender
Chainextender refers to the compound of Han Liangge functional group, and normally small molecules dibasic alcohol, diamine, thanomin etc., in urethane is synthetic, generally by carrying out chain extending reaction production of linear polymer with end NCO base polyurethane prepolymer for use as.Chainextender is small molecules, in polyurethane molecular, hard segment content is produced to contribution.Meeting under curing prerequisite, chainextender consumption is more, and corresponding vulcabond consumption is also more, and the hard segment content of urethane is more, can obtain thus the material of high viscosity, higher hardness.
The present invention's chainextender used is chloro-4, the 4 '-diaminodiphenyl-methane of BDO, 3,3 '-bis-, TriMethylolPropane(TMP), quinhydrones-beta-hydroxyethyl ether, 1, any one in 6-hexylene glycol.Preferably, the present invention uses BDO and/or glycerol.
In A component, the content of chainextender is 1 quality %-20 quality %, preferably 2 quality %-19 quality %?, 5 quality %-15 quality % more preferably.If the content of chainextender is lower than 1 quality %, the cohesiveness of material and hardness do not reach requirement.If higher than 20 quality %, the B material needing can increase accordingly.
The inventor is surprisingly found out that, uses and increases the compression set resistant that chainextender can improve the urethane induration of final acquisition effectively.
4. fire retardant
Fire retardant mainly contains organic and inorganic at present, halogen and non-halogen.Organic is to take some fire retardants that bromine system, phosphorus nitrogen system, nitrogen system and red phosphorus and compound be representative, and inorganic is mainly the flame-retardant systems such as antimonous oxide, magnesium hydroxide, aluminium hydroxide, silicon system.
The present invention's fire retardant used comprises clorafin, trichloroethyl phosphate, three (1-chlorination sec.-propyls), three (1,3-bis-chloro isopropyls) phosphoric acid ester, dimethyl methyl phosphonate, ammonium polyphosphate, triphenylphosphate, melamine polyphosphate (MPP), one or more in zinc borate (FB).Preferably, the present invention uses clorafin, three (1,3-, bis-chloro isopropyls) phosphoric acid ester.
In A component, the content of fire retardant is 5 quality %-20 quality %, preferably 6 quality %-18 quality %?, 8 quality %-15 quality % more preferably.If the content of fire retardant is lower than 5 quality %, flame retardant effect does not reach requirement.If higher than 20 quality %, reduce the ultimate compression strength of material.
5. catalyzer
Catalyzer is that conventional catalyzer mainly contains tertiary amine catalyst and the large class of organometallic compound two in urethane and raw material thereof are synthetic.Amines catalyst is generally used in the production of urethane foam, mainly be divided into following a few class: aliphatics amine catalyzer has N, N-dimethylcyclohexylamine, two (2-dimethylaminoethyl) ether, N, N, N ', N '-tetramethyl-Alkylenediamine, triethylamine, N, N-dimethyl benzylamine etc.Alicyclic amine catalyzer has solid amine, N-ethylmorpholine, N-methylmorpholine, N, N '-diethyl piperazine etc.Alcohol compound catalyzer has trolamine, triethylene diamine etc.Aromatic amine has pyridine, N, N '-lutidine etc.Organometallic compound comprises carboxylate salt, metal alkyl compound etc., and contained metallic element mainly contains tin, potassium, lead, mercury, zinc etc., and the most frequently used is organo-tin compound, comprises dibutyl tin laurate, stannous octoate etc.
Used catalyst of the present invention is N, N-dimethylcyclohexylamine, N-methylmorpholine, triethylamine, N, one or more in N-dimethyl benzylamine, trolamine, stannous octoate, triethylene diamine.Preferably described catalyzer is N-methylmorpholine, N, one or more in N-dimethyl benzylamine and trolamine.
In A component, the content of catalyzer is 0.2 quality %-6 quality %, is preferably 0.2 quality %-5 quality %, more preferably 0.2 quality %-3 quality %.If the content of catalyzer is lower than 0.2 quality %, speed of response is too slow, does not reach requirement.If higher than 5 quality %, speed of reaction is too fast, to construction, bring certain difficulty.
6. softening agent
Softening agent is a kind of flexibility of material or additive of material liquefaction of increasing.
Softening agent is divided into phthalic ester (as: DBP, DOP, DIDP), fatty group dibasic acid (as: Octyl adipate DOA, dioctyl sebacate DOS), phosphoric acid ester (as: Tritolyl Phosphate TCP, phosphate toluene diphenyl ester CDP), epoxy compounds (as: epoxidised soybean oil, epoxyoleic acid butyl ester), Reoplex (as: hexanodioic acid propanediol polyester), benzene polyacid ester (as: 1,2,4-triisooctyl trimellitate), chloro-plasticizer (as: clorafin, pentachloro-methyl stearate), alkyl sulfonic ester etc.
The present invention's softening agent used is one or more in phthalic ester (as: dibutyl phthalate (DBP), dioctyl phthalate (DOP) (DOP), Di Iso Decyl Phthalate (DIDP)), Octyl adipate DOA, phosphate toluene diphenyl ester CDP, alkyl sulfonic ester.Preferably, the present invention uses Octyl adipate DOA, phosphate toluene diphenyl ester CDP.
In A component, the content of softening agent is 5 quality %-10 quality %, is preferably 5.5 quality %-9.5 quality %, more preferably 6 quality %-8 quality %.If the content of softening agent lower than 5 quality %, does not have the effect that increases toughness of material.If higher than 10 quality %, reduce the ultimate compression strength of material.
B component
B component is isocyanic ester or modification derivant matter, isocyanic ester is one of main raw material of polyurethane adhesive, conventional isocyanic ester has tolylene diisocyanate (TDI), ditan-4, 4 ' vulcabond (MDI), liquefied mdi, poly methylene poly phenyl poly isocyanate (PAPI), 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), naphthalene-1, 5-vulcabond (NDI), Methylcyclohexyl diisocyanate (HTDI), dicyclohexyl methane diisocyanate (HMDI) tetramethylxylylene diisocyanate (HMXDI).Modified isocyanate is mainly polyisocyanates performed polymer.One or more that the present invention component B used is above-mentioned substance.Preferably, the present invention uses tolylene diisocyanate, poly methylene poly phenyl poly isocyanate, isophorone diisocyanate.
Below introduce the preparation method of special engineered material for reinforcing of the present invention.
Each material waterproof of A component is mixed and can be made A component.B component can be used commercially available isocyanic ester or modification derivant matter.
Reinforcing of the present invention is that A component and B component are mixed and injected coal (rock) layer after cured according to the volume ratio of 1: 4～4: 1 by the using method of special engineered material.A component and B component through mixing have excellent mobility and cohesiveness, can trickle fast in gap, solidify at short notice, and blind, has strong cohesive force and high compressive strength to coal petrography.
During injection, can adopt Double-liquid mud-injection pump.
Reinforcing of the present invention with special engineered material compared with prior art material cost significantly reduce, temperature of reaction reduces greatly, flame retardant resistance improves, and the urethane induration obtaining after hybrid reaction has superelevation mechanical property, there is low deformation, bearing resistance is high, the feature that tensile strength is large.Deformation is in 10%, and more than bearing resistance can reach 70MPa, tensile strength is greater than 16Mpa.
Accompanying drawing explanation
Fig. 1 is that product carries out the force-displacement curve that compression experiment obtains, peak pressure 160.25KN, ultimate compression strength 81.61Mpa described in embodiment 1.
Embodiment
The present invention will be described to enumerate a part of specific embodiment below, is necessary to be pointed out that at this following examples, only for the present invention is further illustrated, do not represent limiting the scope of the invention.The modification that other people make based on spirit of the present invention and adjustment still belong to protection scope of the present invention.
Embodiment 1
A component is got polyoxypropyleneglycol 31Kg, polyethylene glycol adipate glycol 24Kg, chainextender 3,3 '-bis-chloro-4,4 '-diaminodiphenyl-methane 19Kg, softening agent hexanodioic acid dibutyl ester 5.2Kg, fire retardant zinc borate (FB) 19.3Kg, catalyst n, N-dimethyl benzylamine 1.5Kg, load weighted polyether glycol, polyester polyol, chainextender, softening agent, fire retardant are joined in reactor and stirred, then add catalyzer fully to stir at normal temperatures, be component A.
B component is tolylene diisocyanate.
Get A, B component is uniformly mixed into induration for 1: 1 by volume, under normality operating mode, its performance index are as follows:
Temperature of reaction: 100 ℃
Cohesive strength: 3.1MPa
Tensile strength: 18MPa
Ultimate compression strength: 72MPa
Flame retardant resistance: alcohol blast burner flaming combustion time 0.16s, flameless combustion time 3.7s, spirit lamp flaming combustion time 0.08s, flameless combustion time 2.1s.
Embodiment 2
A component is got polyoxytrimethylene triol 43Kg, poly-adipate glycol propylene glycol ester glycol 19Kg, chainextender quinhydrones-beta-hydroxyethyl ether 14Kg, softening agent hexanodioic acid dibutyl ester 7.4Kg, fire retardant zinc borate (FB) 13.7Kg, catalyst n, N-dimethyl benzylamine 2.9Kg, load weighted polyether glycol, polyester polyol, chainextender, softening agent, fire retardant are joined in reactor and stirred, then add catalyzer fully to stir at normal temperatures, be component A.
B component is tolylene diisocyanate.
Get A, B component is uniformly mixed into induration for 2: 1 by volume, under normality operating mode, its performance index are as follows:
Temperature of reaction: 115 ℃
Cohesive strength: 3.7MPa
Tensile strength: 23MPa
Ultimate compression strength: 75MPa
Flame retardant resistance: alcohol blast burner flaming combustion time 0.33s, flameless combustion time 5.2s, spirit lamp flaming combustion time 0.28s, flameless combustion time 4.7s.
Embodiment 3
A component is got TriMethylolPropane(TMP) polyethers 59Kg, poly-hexanodioic acid glycol ether esterdiol 10Kg, chainextender quinhydrones-beta-hydroxyethyl ether 8Kg, softening agent phosphate toluene diphenyl ester 8.9Kg, fire retardant clorafin 9.5Kg, catalyst n-methylmorpholine 4.6Kg, load weighted polyether glycol, polyester polyol, chainextender, softening agent, fire retardant are joined in reactor and stirred, then add catalyzer fully to stir at normal temperatures, be component A.
B component is tolylene diisocyanate.
Get A, B component is uniformly mixed into induration for 1: 2 by volume, under normality operating mode, its performance index are as follows:
Temperature of reaction: 127 ℃
Cohesive strength: 5.8MPa
Tensile strength: 29MPa
Ultimate compression strength: 81MPa
Flame retardant resistance: alcohol blast burner flaming combustion time 0.65s, flameless combustion time 7.5s, spirit lamp flaming combustion time 0.6s, flameless combustion time 6.8s.
Embodiment 4
A component is got polytetrahydrofuran diol 74Kg, poly-hexanodioic acid-1,4-butanediol ester glycol 6Kg, chainextender quinhydrones-beta-hydroxyethyl ether 3Kg, softening agent hexanodioic acid dibutyl ester 5.3Kg, fire retardant clorafin 5.9Kg, catalyst n, N-dimethyl benzylamine 5.8Kg, load weighted polyether glycol, polyester polyol, chainextender, softening agent, fire retardant are joined in reactor and stirred, then add catalyzer fully to stir at normal temperatures, be component A.
B component is tolylene diisocyanate.
Get A, B component is uniformly mixed into induration for 4: 1 by volume, under normality operating mode, its performance index are as follows:
Temperature of reaction: 136 ℃
Cohesive strength: 6.4MPa
Tensile strength: 34MPa
Ultimate compression strength: 88MPa
Flame retardant resistance: alcohol blast burner flaming combustion time 0.85s, flameless combustion time 8s, spirit lamp flaming combustion time 0.8s, flameless combustion time 7s.
Embodiment 5-15
Claims (10)
1. the special engineered material of reinforcing, is characterized in that, described reinforcing is comprised of A component and B component with special engineered material, and the volume ratio of described A component and B component is 1: 4～4: 1; Wherein said A component comprises: polyether glycol 30-80 mass parts, polyester polyol 5-25 mass parts, chainextender 1-20 mass parts, fire retardant 5-20 mass parts, softening agent 5-10 mass parts, catalyzer 0.2-6 mass parts; Described B component is isocyanic ester and/or its modification derivant.
2. the special engineered material of reinforcing as claimed in claim 1, is characterized in that, the molecular weight of described polyether glycol is 200-3000, hydroxyl value 50～700mKOH/g, acid number≤0.15mKOH/g, viscosity 50～800mPas.
3. the special engineered material of reinforcing as claimed in claim 1 or 2, it is characterized in that, described polyether glycol selects one or more in the group that free polyoxypropyleneglycol, polyoxytrimethylene triol, TriMethylolPropane(TMP) polyethers, polytetrahydrofuran diol and tetrahydrofuran (THF)-propylene oxide copolymerization glycol form.
4. the special engineered material of reinforcing as claimed in claim 1, it is characterized in that, the viscosity of described polyester polyol is 50～800mPas, hydroxyl value 30-600mKOH/g, acid number≤0.15mKOH/g, moisture < 0.1%, and be preferably selected from by polyethylene glycol adipate glycol, poly-adipate glycol propylene glycol ester glycol, poly-hexanodioic acid glycol ether esterdiol, poly-adipate glycol glycol ether esterdiol, poly-hexanodioic acid-1, 4-butanediol ester glycol, poly-adipate glycol-1, 4-butanediol ester glycol, poly-hexanodioic acid neopentyl glycol-1, 6-hexylene glycol esterdiol, poly-hexanodioic acid Viscotrol C ester polyol, poly--6-caprolactone glycol, poly-carbonic acid 1, one or more in the group that the own-ol esterdiol of 6-forms.
5. the special engineered material of reinforcing as claimed in claim 1, it is characterized in that, described chainextender is 1,4-butyleneglycol, 3,3 '-bis-chloro-4,4 '-diaminodiphenyl-methanes, TriMethylolPropane(TMP), quinhydrones-beta-hydroxyethyl ether, 1, any one in 6-hexylene glycol, preferably described chainextender is BDO and/or glycerol.
6. the special engineered material of reinforcing as claimed in claim 1, it is characterized in that, described fire retardant selects free clorafin, trichloroethyl phosphate, three (1-chlorination sec.-propyls), three (1,3-bis-chloro isopropyls) phosphoric acid ester, dimethyl methyl phosphonate, ammonium polyphosphate, triphenylphosphate, melamine polyphosphate (MPP), one or more in the group that zinc borate (FB) forms, preferably described fire retardant be in clorafin, three (1,3-, bis-chloro isopropyls) phosphoric acid ester and zinc borate (FB) one or more.
7. the special engineered material of reinforcing as claimed in claim 1, it is characterized in that, one or more in the described softening agent choosing group that freely phthalic esters such as dibutyl phthalate (DBP), dioctyl phthalate (DOP) (DOP), Di Iso Decyl Phthalate (DIDP), Octyl adipate, phosphate toluene diphenyl ester, alkyl sulfonic ester form, preferably described softening agent is Octyl adipate and/or phosphate toluene diphenyl ester.
8. the special engineered material of reinforcing as claimed in claim 1, it is characterized in that, described catalyzer selects free N, N-dimethylcyclohexylamine, N-methylmorpholine, triethylamine, N, one or more in the group that N-dimethyl benzylamine, trolamine, stannous octoate, triethylene diamine form, preferably described catalyzer is N-methylmorpholine, N, one or more in N-dimethyl benzylamine and trolamine.
9. the special engineered material of reinforcing as claimed in claim 1, it is characterized in that, described isocyanic ester selects free tolylene diisocyanate, ditan-4, 4 ' vulcabond, liquefaction ditan-4, 4 ' vulcabond, poly methylene poly phenyl poly isocyanate, 1, hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1, 5-vulcabond, Methylcyclohexyl diisocyanate, one or more in the group that dicyclohexyl methane diisocyanate and tetramethylxylylene diisocyanate form, the modification derivant of described isocyanic ester is polyisocyanates performed polymer, and preferably described isocyanic ester selects one or more in the group that free tolylene diisocyanate, poly methylene poly phenyl poly isocyanate and isophorone diisocyanate form.
10. the preparation method of special engineered material for the reinforcing described in any one in claim 1～9, it is characterized in that, each material waterproof of A component is mixed to prepare A component, during use, A component and B component are waited to solidify according to volume ratio mixing injection coal seam and/or the rock stratum of 1: 4～4: 1.
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| CN102558498A (en) * | 2012-01-04 | 2012-07-11 | 山西兆信生物科技有限公司 | Polyurethane reinforcing and filling materials for coal mine |
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