CN101775120A - Curing agent diisocyanate prepolymer and preparation method thereof - Google Patents
Curing agent diisocyanate prepolymer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a curing agent diisocyanate prepolymer and a preparation method thereof. The preparation method comprises the following steps: 4, 4-MDI or HDI and organic solvent are added into a reactor and are heated to be smelted and uniformly mixed, and dehydrated dibasic alcohol is added to be reacted at the temperature 50 to 100 DEG C for 1 to 6 hours so as to obtain the MDI or HDI modifier; being cooled down to 50 DEG C, the mixture of polyatomic alcohol and organic solvent are divided to add and are reacted at the temperature of 50 to 100 DEG C for 2 to 6 hours; and being cooled down to 60 DEG C, an MDI or HDI prepolymer curing agent can be prepared. The method of the diisocyanate manufacture-series prepolymer curing agent is innovated, the molecular structure of the curing agent can be designed according to different requirements of the user, and the curing agent can be used for supporting the main agent such as two-pack polyurethane coating and adhesive. The curing agent diisocyanate prepolymer has simple process and good storage property, and also has the advantages that high solid content can be obtained.
Description
Technical field
The present invention relates to a kind of polyurethane coating, adhesive solidification agent prepolymer and preparation method thereof, is a kind of vulcabond 4 of symmetrical configuration specifically, 4 '-MDI or the agent of HDI prepolymer cures and preparation method thereof.
Background technology
The diisocyanate monomer of a large amount of uses of selling on the market can not directly be used as the solidifying agent of polyurethane coating, tackiness agent, it at room temperature is the tolylene diisocyanate (TDI), 1 of liquid, the vapour pressure height of hexamethylene-diisocyanate (HDI), rate of volatilization is fast, gas phase toxicity is big, influence the healthy of production operation personnel, and environment is polluted; At room temperature be that (4,4 '-MDI) steam forces down the solid diphenylmethanediisocyanate, and the gas phase volatility is very little, and is inconvenient but it uses, and also be easy to generate dipolymer in storage process, and package stability is poor.Generally need vulcabond is made the prepolymer cures agent, could solve simultaneously its at room temperature toxicity big, use problems such as manufacturability difference and package stability difference.The patent documentation report and that generally adopt both at home and abroad at present several vulcabond are made the method for solidifying agent: the one, and the classical way of solidifying agent is made in TDI and TriMethylolPropane(TMP) reaction, the 2nd, the HDI Biuret Method, the 3rd, TDI, HDI, IPDI tripolymer method, the 4th, liquefied mdi method.All multi-methods all exist certain pros and cons, and especially 4 of symmetrical configuration, 4 '-MDI, HDI, their two NCO group activity are identical, and two-NCO base is participated in reaction easily simultaneously and is generated gelling material, and difficulty of processing is very big.Usually HDI is processed into biuret and tripolymer in the world, its manufacturing process complexity, apparatus expensive, production efficiency is low, and these two kinds of products of China's use at present also mainly rely on import.4, the liquefied mdi kind that 4 '-MDI makes is single, and performance is lower, can only be used in aspects such as polyurethane foam, cast.How bar structure symmetric 4,4 '-MDI is processed into the solidifying agent of polyurethane coating and tackiness agent, up to the present also do not find a kind of practicable method in the world, the fragrant same clan diisocyanate curing agent that uses in polyurethane coating and adhesive industry still is the bigger TDI solidifying agent of toxicity.
For this reason, the researchist of urethane industry is making great efforts exploring new manufacture method, has seen in the document at home with 4, and 4 '-MDI makes the following report of coating curing agent:
Chinese invention patent ublic specification of application CN1116327C discloses a kind of coating curing agent 4 on July 30th, 2003,4 '-biphenyl methane diisocyanate prepolymer and preparation method thereof, its patent No. is 00127691.3, introduce it and make 4, the main points of 4 '-MDI solidifying agent are: react under 230-245 ℃ of high temperature with Viscotrol C and TriMethylolPropane(TMP) and make TriMethylolPropane(TMP) list castor-oil plants oleic acid ester, behind organic solvent dimethylbenzene, pimelinketone reflux dewatering, again with 4, it is 45% prepolymer that 4 '-MDI reaction makes solid content.Its signal modular construction formula is:
The deficiency that this invention exists is: link 4 with Viscotrol C, 4 '-MDI and TriMethylolPropane(TMP), the intensity that the MDI solidifying agent of making is given goods is lower, kind is single, and application surface is narrow, far can not satisfy the demand of market polyurethane coating, the various performances of tackiness agent, and its complicated process of preparation, the temperature of reaction height is also made medium with noxious solvent dimethylbenzene, and the product solid content is also lower.
How to solve 4 of symmetrical configuration, 4 '-MDI, HDI make the technical problem of coating and adhesive solidification agent, are meanings of the present invention.
Summary of the invention
The object of the present invention is to provide a kind of curing agent diisocyanate prepolymer and preparation method thereof, with a kind of convenience, be suitable for, economic method is 4,4 '-MDI or HDI and different dibasic alcohol and polyol reactions make a series of diisocyanate prepolymer solidifying agent that are applicable to coating, tackiness agent with different performance.
Innovative point of the present invention is to be 200710051412.8 1 kinds of solidifying agent 4 at the Chinese invention patent application number, 4 ' biphenyl methane diisocyanate prepolymer and preparation method thereof and 200710051761.X solidifying agent 1, on the basis of hexamethylene-diisocyanate prepolymer and preparation method thereof, the scope of dibasic alcohol is expanded to the small molecules dibasic alcohol and contains the oligopolymer of two active hydrogens from original long chain diol, expand the scope of polyvalent alcohol to polyvalent alcohol from TriMethylolPropane(TMP) with three and three above hydroxyls.
The present invention catches 4,4 '-MDI and HDI symmetrical configuration, two NCO groups active identical be the key problem in technology of making the solidifying agent difficult point, by introducing the reaction earlier of dibasic alcohol and part vulcabond, generating portion modification vulcabond, the activity decline of modification vulcabond, constituted in the system activity difference between the molecule, when continuing with polyol reaction, therefore the speed of response faster or slower of each molecule can prevent to produce gel.The principle of the invention has been innovated the manufacturing technology of existing document and ordinary method.
Product of the present invention is a kind of mixed prepolymer, and its signal modular construction formula is:
Wherein: R is alkyl, phenyl or the ethers of dibasic alcohol, the compound of ester class; R
1For ternary and more than the ternary alcohol alkyl, phenyl or derivatives thereof; M is 4, and structural formula is during 4 '-MDI:
Structural formula was when M was HDI: (CH
2)
6
Product index of the present invention following (following content all is weight percentage):
(1) outward appearance: colourless to light yellow transparent liquid;
(2) solid content: 30～80%;
(3) NCO content: 9～18% (in total solidss);
(4) storage period: half a year.
Preparation method of the present invention and step thereof comprise:
A, in reactor, add vulcabond and organic solvent, be warming up to about 60 ℃ it is dissolved and stir evenly, add dibasic alcohol,, make the vulcabond modifier 50～100 ℃ of reactions 1～6 hour through dehydration; B, be cooled to about 50 ℃, gradation adds the mixture of polyvalent alcohol and organic solvent, and at 50～100 ℃, insulation reaction 2～6 hours is cooled to 60 ℃; C, add an amount of organic solvent, stir by the requirement of product solid content, discharging, MDI or the agent of HDI prepolymer cures;
Wherein each reactant consumption is as follows by weight percentage:
4,4 '-MDI or HDI 40～86%
Dibasic alcohol 4～45%
Polyvalent alcohol 5～21%
The weight ratio of consumption of organic solvent and reactant consumption is 7～2: 3～8.
The vulcabond that adds described in the step a is 4, wherein any of 4 '-MDI, HDI.4,4 '-MDI is 4, and 4 '-diphenylmethanediisocyanate, HDI are hexamethylene diisocyanates.
Dibasic alcohol described in the step a is polyester diol, polyether Glycols, other dibasic alcohol, small molecules dibasic alcohol and the oligopolymer that contains two active hydrogens, as poly-m-phthalic acid-hexanodioic acid-neopentyl glycol-hexylene glycol esterdiol, poly-epsilon-caprolactone glycol, polycarbonate diol, polyoxypropyleneglycol, polytetrahydrofuran diol, Synolac glycol, polybutadiene diol, Polybutadiene-acrylonitrile copolymerization glycol, 3-methyl isophthalic acid, at least a material that contains dihydroxylic in the 5-pentanediol micromolecular dibasic alcohol.
Polyvalent alcohol described in the step b is the polyvalent alcohol with three and three above hydroxyls, as TriMethylolPropane(TMP), trimethylolethane, glycerol, 1,2, and at least a in 6-hexanetriol, the tetramethylolmethane.
The chemical equation that vulcabond and diol reaction make the vulcabond modifier is:
The chemical equation that vulcabond modifier, vulcabond and polyol reaction make diisocyanate prepolymer is:
Wherein: R is alkyl, phenyl or the ethers of dibasic alcohol, the compound of ester class; R
1For ternary and more than the ternary alcohol alkyl, phenyl or derivatives thereof; M is 4, and structural formula is during 4 '-MDI:
Structural formula was when M was HDI: (CH
2)
6
From above-mentioned chemical equation (A) as can be seen: vulcabond and diol reaction, the vulcabond modifier of generation two ends headband NCO group, it has changed the activity of vulcabond.The dibasic alcohol difference that adds, the active degree that descends of the vulcabond modifier of generation is also different.
From (B) formula as can be seen: when vulcabond modifier, vulcabond and polyol reaction, the lack of alignment sterically hindered and big and small molecule that the R base produces increases the randomness of system, the molecule activity resistance strengthens, the vulcabond modifier is active simultaneously reduces, and the activity of vulcabond itself does not change, the chemical reaction velocity of different activities molecule is inequality like this, thereby has formed the orderly reaction of speed, has avoided the incidental gel reaction of identical bioactive molecule.Because the randomness of molecule strengthens and makes the crystallinity of system descend in the prepolymer, so the isocyanate curing agent that produces has lower viscosity, and also is difficult to recrystallization in depositing process.
The present invention makes 4 with tradition, the difference of 4 '-MDI, HDI solidifying agent method is: introduced the dibasic alcohol manufacturing technology in solidifying agent, dibasic alcohol has changed the structure of vulcabond, reduced its activity, make that the activity of vulcabond has nothing in common with each other in the system, form the difference of chemical reaction velocity, thereby avoided the gel reaction generation.The invention solves 4,4 ' MDI, HDI direct and the ternary and the above pure easily difficult problem of formation gel of reacting of ternary of symmetrical configuration.Because the above alcohol of dibasic alcohol, ternary and ternary is various in style, the proportioning variation range of constituent is wide, so MDI of the present invention, HDI prepolymer kind diversification can satisfy the needs of polyurethane coating, tackiness agent various uses, different performance feature.
The used organic solvent of the present invention is vinyl acetic monomer, N-BUTYL ACETATE, propylene glycol monomethyl ether acetate ester class, butanone, pimelinketone ketone, toluene, dimethylbenzene aromatic hydrocarbons, dioxane, tetrahydrofuran (THF), N, dinethylformamide reaches wherein two or more mixture.
The present invention compared with prior art has following advantage: one, the present invention is with 4 of dibasic alcohol and polyvalent alcohol and symmetrical configuration, the novel method of solidifying agent is made in 4 '-MDI, HDI reaction, enlarged the content of Chinese invention patent 200710051412.8,200710051761.X, broken the ordinary method of traditional manufacturing MDI, HDI solidifying agent, the manufacturing technology of introducing with existing patent documentation is different fully.Two, toxicity is low.4 of the present invention's production, 4 '-MDI solidifying agent do not have the free monomer of removal operation, compare noresidue monomer environmental pollution problem with the TDI solidifying agent of traditional method manufacturing.Three, technology advanced person.Whole chemical reaction of the present invention carries out under 100 ℃ of water-baths, and energy consumption is low, and technology is simple, production efficiency height, three-waste free discharge.Four, excellent storage stability.4 of the present invention's manufacturing, solidifying agent gluing or spoilage problems that the dimerization of 4 '-MDI prepolymer cures agent isocyanate-free in depositing process and trimerization reaction bring.Five, solid content height.Viscosity of the present invention is low, and solid content can be up to 80%, and is easy to use.Six, applied widely.Select different dibasic alcohol, different polyvalent alcohol and different constituent proportionings, can be made into a series of MDI, the agent of HDI prepolymer cures, the kind of diversification can satisfy the various demands of supporting double-component polyurethane coating, tackiness agent host.
In order to implement the present invention better, the present invention is further illustrated now to enumerate following embodiment.
Embodiment
Embodiment 1
A, add 4 of 250 gram fusings in reactor, 4 '-MDI and 60 gram vinyl acetic monomers are warming up to 50 ℃, add 7 gram neopentyl glycol and 8 gram glycol ethers through dehydration, 50～60 ℃ of reactions 1.5 hours, and 70～80 ℃ of reactions 2 hours; B, be cooled to 50 ℃, drip the mixed solution that 31 gram TriMethylolPropane(TMP)s and 30 gram vinyl acetic monomers are formed, dripped off in 2 hours, 50～60 ℃ of reactions 1 hour, 70～80 ℃ of reactions 2 hours, 80～90 ℃ were reacted 1.5 hours, and were cooled to 60 ℃; C, adding 9 gram N-BUTYL ACETATEs stir, and it is that 75% viscosity is the MDI solidifying agent of 3800mpa.s (25 ℃) that discharging gets 395 gram solid contents.The NCO content of this solidifying agent is 10.5% (counting 14.3% with total solids) after testing.
Annotate: 1, detect solid content and undertaken by State Standard of the People's Republic of China's " mensuration of GB/T 2793-1995 tackiness agent non-volatile content ".
2, detecting NCO content is undertaken by People's Republic of China's chemical industry standard " isocyanate group Determination on content in the HG/T 2409-92 base polyurethane prepolymer for use as ".
3, detecting viscosity is undertaken by State Standard of the People's Republic of China's " mensuration of GB/T 2794-1995 tackiness agent viscosity ".
Embodiment 2
A, in reactor, add 4 of 200 gram fusings, 4 '-MDI and 50 gram vinyl acetic monomers are warming up to 60 ℃, add the poly-m-phthalic acid-hexanodioic acid of the 80 grams-neopentyl glycol-hexylene glycol esterdiol through dehydration, 50～60 ℃ of reactions 1 hour, 70～80 ℃ were reacted 2 hours; B, be cooled to 50 ℃, drip the mixed solution that 28 gram TriMethylolPropane(TMP)s and 30 gram vinyl acetic monomers are formed, dripped off in 1.5 hours, 50～60 ℃ of reactions 1 hour, 70～80 ℃ of reactions 1 hour, 80～90 ℃ were reacted 1.5 hours, and were cooled to 60 ℃; C, add 13 gram toluene, 10 gram N-BUTYL ACETATEs, stir, it is 75% MDI solidifying agent that discharging gets 411 gram solid contents.The NCO content of this solidifying agent is 8% (counting 10.7% with total solids) after testing.
Embodiment 3
A, in reactor, add 200 gram HDI and 30 gram vinyl acetic monomers, be warming up to 60 ℃, adding is through 64 gram polycarbonate diols of dehydration, at room temperature cold stirring 0.5 hour, be warmed up to 60～70 ℃ of reactions 1 hour, add 6 gram 3-methyl isophthalic acids again, the 5-pentanediol, 50～60 ℃ of reactions 1 hour, 70～80 ℃ were reacted 1.5 hours; 80～90 ℃ were reacted 0.5 hour; B, be cooled to 50 ℃, drip the mixed solution that 42 gram TriMethylolPropane(TMP)s and 40 gram vinyl acetic monomers are formed, dripped off in 2.5 hours, be warming up to 70～80 ℃ of reactions 2 hours, 80～90 ℃ were reacted 1.5 hours, and were cooled to 60 ℃; C, add 14 gram N-BUTYL ACETATEs and 20 gram propylene glycol monomethyl ether acetate, stir, it is 75% HDI solidifying agent that discharging gets 416 gram solid contents.The NCO content of this solidifying agent is 12.2% (counting 16.3% with total solids) after testing.
Embodiment 4
A, add 4 of 280 gram fusings in reactor, 4 '-MDI and 150 gram vinyl acetic monomers are warming up to 60 ℃, add 180 gram polytetrahydrofuran diols through dehydration, 50～60 ℃ of reactions 2.5 hours, 70～80 ℃ of reactions 1.5 hours, 80～90 ℃ of reactions 1.5 hours; B, be cooled to 45 ℃, divide to add 33 grams 1,2 for four times, the mixed solution that 6-hexanetriol and 40 gram vinyl acetic monomers are formed added in 1.5 hours, 45～55 ℃ of reactions 1 hour, and 65～75 ℃ of reactions 2 hours, 85～95 ℃ were reacted 1.5 hours, and were cooled to 60 ℃; C, add 84 toluene and 54 gram N-BUTYL ACETATEs, stir, it is 60% MDI solidifying agent that discharging gets 821 gram solid contents.
Embodiment 5
A, in reactor, add 4 of 300 gram fusings, 4 '-MDI and 60 gram vinyl acetic monomers, be warming up to 60 ℃, adding is through 13.6 gram Rutgers 612s of dehydration, 50～60 ℃ of reactions 1 hour, add 11 gram 3-methyl isophthalic acids again, the 5-pentanediol, 50～60 ℃ of reactions 1.5 hours, 70～80 ℃ were reacted 2.5 hours; B, be cooled to 45 ℃, divide to add the mixed solution that 35 gram TriMethylolPropane(TMP)s and 40 gram vinyl acetic monomers are formed for four times, added in 1.5 hours, 50～60 ℃ of reactions 1.5 hours, 70～80 ℃ of reactions 2 hours, 85～95 ℃ were reacted 0.5 hour, and were cooled to 60 ℃; C, add 21 gram vinyl acetic monomers, stir, it is 75% MDI solidifying agent that discharging gets 480 gram solid contents.
Embodiment 6
A, add 4 of 250 gram fusings in reactor, 4 '-MDI and 60 gram vinyl acetic monomers are warming up to 60 ℃, add 80 gram poly-epsilon-caprolactone glycol through dehydration, 60～70 ℃ of reactions 3 hours, and 80～90 ℃ of reactions 2 hours; B, be cooled to 60 ℃, drip the mixed solution that 33.6 gram trimethylolethanes and 40 gram vinyl acetic monomers are formed, added in 2 hours, 60～70 ℃ of reactions 1.5 hours, 70～80 ℃ of reactions 1.5 hours rose to 80～90 ℃ again and reacted 1 hour, are cooled to 60 ℃; C, adding 21 gram vinyl acetic monomers stir, and it is that 75% viscosity is the MDI solidifying agent of 5500mpa.s (25 ℃) that discharging gets 485 gram solid contents.
Embodiment 7
A, in reactor, add 220 gram HDI and 50 gram vinyl acetic monomers, be warming up to 60 ℃, add 11 gram butyl ethyl propylene glycol and 10 gram neopentyl glycol through dehydration, 50～60 ℃ of reactions 2 hours, 70～80 ℃ of reactions 2 hours; B, be cooled to 50 ℃, drip the mixed solution that 33 gram tetramethylolmethanes and 70 gram vinyl acetic monomers are formed, dripped off in 2 hours, 50～60 ℃ of reactions 1.5 hours, 70～80 ℃ of reactions 1.5 hours, 80～90 ℃ were reacted 1 hour, and were cooled to 60 ℃; C, add 84 gram N-BUTYL ACETATEs and 70 gram propylene glycol monomethyl ether acetate, stir, it is 50% HDI solidifying agent that discharging gets 548 gram solid contents.
Application Example 1
Product 40 grams of embodiment 2 and hydroxyl component 100 grams of PU coating mix, and the coating lacquer film properties that makes is as follows: dryness: 25 ℃, surface drying time 40 minutes is done solid work 4 hours time; Test performance after 2 days: gloss (60 °): 〉=95%; Hardness: Shao Shi D55; Shock strength: 480N.cm; Sticking power: 1 grade; Snappiness: 1mm.
The method of inspection: gloss is pressed GB9754-88, hardness and is pressed GB1730-79, shock strength and press that GB1732-93, sticking power press GB1720-89, snappiness is pressed the GB1731-79 standard.
Application Example 2
Product 40 grams of embodiment 3 and 100 gram Hydroxylated acrylic resin solution mix, and the coating lacquer film properties that makes is as follows: dryness: 25 ℃, surface drying time 50 minutes is done solid work 12 hours time; Test performance after 7 days: gloss (60 °): 〉=95%; Hardness 〉=Shao Shi D35; Shock strength: 416N.cm; Sticking power: 1 grade; Snappiness: 1mm.
Application Example 3
Product 40 grams of embodiment 5 and package compound are mixed with hydroxyl component 100 grams of polyurethane adhesive, be used for the compound of pure aluminum foil and CPP film, in 50 ℃ solidify 48 hours after, carry out T type peeling strength test by GB/T 2791-1995 " tackiness agent T peeling strength test method flexible material is to flexible material ", stripping strength is 1150g/15mm, and the laminated film behind cooking test does not find that film has separation phenomenon.
Application Example 4
Product 40 grams of embodiment 6 and package compound are mixed with hydroxyl component 100 grams of polyurethane adhesive, be used for the compound of PET aluminium plating film and CPP film, the performance that makes composite membrane is as follows: solidify under 25 ℃ of room temperatures 8 hours can the branch sanction, in 50 ℃ solidify 24 hours after, press GB/T 2790-1995 " 180 ° of peeling strength test methods of tackiness agent, flexible material is to rigid material " carry out 180 ° of peeling strength tests, the PET aluminium plating film is torn.
Claims (6)
1. curing agent diisocyanate prepolymer is characterized in that:
Its signal modular construction formula is:
With
With
Wherein: R is alkyl, phenyl or the ethers of dibasic alcohol, the compound of ester class; R
1For ternary and more than the ternary alcohol alkyl, phenyl or derivatives thereof; M is 4, and structural formula is during 4 '-MDI:
Structural formula was when M was HDI: (CH
2)
6
Product index of the present invention is as follows, and following content is weight percentage:
(1) outward appearance: colourless to light yellow transparent liquid;
(2) solid content: 30～80%;
(3) NCO content: 9～18%, in total solids.
2. the preparation method of the described curing agent diisocyanate prepolymer of claim 1, its step comprises:
A, in reactor, add vulcabond and organic solvent, be warming up to about 60 ℃ it is dissolved and stir evenly, add dibasic alcohol,, make the vulcabond modifier 50～100 ℃ of reactions 1～6 hour through dehydration;
B, be cooled to about 50 ℃, gradation adds the mixture of polyvalent alcohol and organic solvent, and at 50～100 ℃, insulation reaction 2～6 hours is cooled to 60 ℃;
C, add an amount of organic solvent, stir by the requirement of product solid content, discharging, MDI or the agent of HDI prepolymer cures;
Wherein each reactant consumption is as follows by weight percentage:
4,4 '-MDI or HDI 40～86%
Dibasic alcohol 4～45%
Polyvalent alcohol 5～21%
The weight ratio of consumption of organic solvent and reactant consumption is 7～2: 3～8.
3. the preparation method of a kind of curing agent diisocyanate prepolymer according to claim 2, it is characterized in that: the vulcabond that adds described in the step a is 4,4 '-diphenylmethanediisocyanate, or hexamethylene diisocyanate.
4. the preparation method of a kind of curing agent diisocyanate prepolymer according to claim 2, it is characterized in that: the dibasic alcohol described in the step a is a polyester diol, polyether Glycols, other dibasic alcohol, small molecules dibasic alcohol and contain the oligopolymer of two active hydrogens, as poly-m-phthalic acid-hexanodioic acid-neopentyl glycol-hexylene glycol esterdiol, the poly-epsilon-caprolactone glycol, polycarbonate diol, polyoxypropyleneglycol, polytetrahydrofuran diol, the Synolac glycol, polybutadiene diol, Polybutadiene-acrylonitrile copolymerization glycol, the 3-methyl isophthalic acid, at least a material that contains dihydroxylic in the 5-pentanediol micromolecular dibasic alcohol.
5. the preparation method of a kind of curing agent diisocyanate prepolymer according to claim 2, it is characterized in that: the polyvalent alcohol described in the step b is the polyvalent alcohol with three and three above hydroxyls, as TriMethylolPropane(TMP), trimethylolethane, glycerol, 1,2, at least a in 6-hexanetriol, the tetramethylolmethane.
6. the preparation method of a kind of curing agent diisocyanate prepolymer according to claim 2, it is characterized in that: the organic solvent described in the step c is vinyl acetic monomer, N-BUTYL ACETATE, propylene glycol monomethyl ether acetate ester class, butanone, cyclohexanone ketone, toluene, dimethylbenzene aromatic hydrocarbons, dioxane, tetrahydrofuran (THF) or N, dinethylformamide reaches wherein two or more mixture.
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Application publication date: 20100714 |