CN101792402B - Isocyanate alkyl substituted cyclohexane and preparation method as well as application thereof - Google Patents
Isocyanate alkyl substituted cyclohexane and preparation method as well as application thereof Download PDFInfo
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- CN101792402B CN101792402B CN200910008599.2A CN200910008599A CN101792402B CN 101792402 B CN101792402 B CN 101792402B CN 200910008599 A CN200910008599 A CN 200910008599A CN 101792402 B CN101792402 B CN 101792402B
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Abstract
The invention relates to a compound shown in formula Ia or Ib, wherein one of p and q is equal to 0, and the other one of p and q is equal to 1; m and y are respectively equal to integers from 0 to 12 independently, and the sum of m and y is equal to 12; and n and x are respectively equal to integers from 0 to 12 independently, and the sum of n and x is equal to 12. The invention also relates to a preparation method of the compound shown in formula Ia or Ib and application of the compound shown in formula Ia or Ib as a component for producing polyurethane lacquer, paint, elastomers, adhesives, textile finishing agents or rocket propellants.
Description
Technical field
The present invention relates to the hexanaphthene that isocyanate-containing alkyl replaces, the invention still further relates to the preparation method of the hexanaphthene that this isocyanate-containing alkyl replaces and their purposes.
Background technology
Aliphatic isocyanates, 1-amyl group-2-heptyl-3 for example, 4-bis-(9-isocyanic ester nonyl)-hexanaphthene (referred to as DDI1410) is the important component of producing polyurethane lacquer, coating, elastomerics, tackiness agent, textile finshing agent, rocket propellant etc.
In the document of having retrieved, mainly contain by low-molecular-weight lipid acid or amine and prepare corresponding isocyanic ester, 1-amyl group-2-heptyl-3 for example, the method for making of 4-bis-(9-isocyanic ester nonyl)-hexanaphthene (DDI1410), but generally all adopt phosgenation to be prepared.The shortcoming of phosgenation is that processing condition are harsh, toxicity large, be difficult for industrialization, yield is low, easily side reaction occurs, to aftertreatment, make troubles, reacting between the isocyanic ester generating as easy generation and raw material amine.
The preparation method of the aliphatic isocyanates of development of new and their applicable suitability for industrialized production, remains those skilled in the art and makes great efforts the research topic of exploring.
Summary of the invention
The cyclohexanes compound that the inventor replaces isocyanate-containing alkyl is that isocyanate ester compound has carried out research extensively and profoundly, result is surprisingly found out that the aliphatic isocyanates of another kind of novelty, with 1-amyl group-2-heptyl-3, hexanaphthene and isomers thereof that the isocyanate-containing alkyl that 4-bis-(8-isocyanic ester octyl group)-hexanaphthene (referred to as PRO1401) is representative replaces, it is the same excellent performance of DDI1410 that the hexanaphthene that this kind isocyanate alkyl that the present invention finds replaces has with another aliphatic isocyanates, to produce polyurethane lacquer, coating, elastomerics, tackiness agent, textile finshing agent, the important component of rocket propellant etc.In addition, the present invention finds, the hexanaphthene that uses sodiumazide legal system to replace for isocyanate-containing alkyl of the present invention have processing condition gentleness, reagent toxicity low, be easy to industrialization, the advantage such as yield is high, side reaction is few, convenient post-treatment.
Summary of the invention:
First aspect present invention relates to following formula Ia or formula Ib compound:
Wherein,
One in p and q is 0, and another is 1;
M and y are 0 to 12 integer independently of one another, and m+y=12;
N and x are 0 to 12 integer independently of one another, and n+x=12.
First aspect present invention provides with following formula Ia or formula Ib compound:
Wherein,
One in p and q is 0, and another is 1;
M and y are 0 to 12 integer independently of one another, and m+y=12;
N and x are 0 to 12 integer independently of one another, and n+x=12,
And precondition is that this formula Ia or formula Ib compound do not comprise 1-hexyl-2-octyl group-3,4-bis-(7-isocyanic ester heptyl)-hexanaphthene.
In an embodiment of formula Ia described in first aspect present invention or formula Ib compound, wherein,
One in p and q is 0, and another is 1;
M and y are 4 to 8 integer independently of one another, and m+y=12;
N and x are 4 to 8 integer independently of one another, and n+x=12.
In an embodiment of formula Ia described in first aspect present invention or formula Ib compound, wherein,
One in p and q is 0, and another is 1;
M is 5,7 or 8, and m+y=12;
N is 5,6,7 or 8, and n+x=12.
In an embodiment of formula Ia compound described in first aspect present invention, wherein
P is that 1, q is 0;
M and y are 4 to 8 integer independently of one another, and m+y=12;
N and x are 4 to 8 integer independently of one another, and n+x=12.
In an embodiment of formula Ia compound described in first aspect present invention, wherein
P is that 0, q is 1;
M and y are 4 to 8 integer independently of one another, and m+y=12;
N and x are 4 to 8 integer independently of one another, and n+x=12.
In an embodiment of formula Ib compound described in first aspect present invention, wherein
P is that 1, q is 0;
M and y are 4 to 8 integer independently of one another, and m+y=12;
N and x are 4 to 8 integer independently of one another, and n+x=12.
In an embodiment of formula Ib compound described in first aspect present invention, wherein
P is that 0, q is 1;
M and y are 4 to 8 integer independently of one another, and m+y=12;
N and x are 4 to 8 integer independently of one another, and n+x=12.
In an embodiment of formula Ia compound described in first aspect present invention, wherein p is that 1, q is 0; And:
M=8, n=6, x=6 and y=4,
M=7, n=5, x=7 and y=5,
M=8, n=8, x=4 and y=4, or
M=5, n=5, x=7 and y=7.
In an embodiment of formula Ia compound described in first aspect present invention, wherein p is that 0, q is 1; And:
M=8, n=8, x=4 and y=4,
M=7, n=7, x=5 and y=5,
M=8, n=6, x=6 and y=4, or
M=5, n=7, x=5 and y=7.
In an embodiment of formula Ib compound described in first aspect present invention, wherein p is that 1, q is 0; And:
M=8, n=6, x=6 and y=4,
M=7, n=5, x=7 and y=5,
M=8, n=8, x=4 and y=4, or
M=5, n=5, x=7 and y=7.
In an embodiment of formula Ib compound described in first aspect present invention, wherein p is that 0, q is 1; And:
M=8, n=8, x=4 and y=4,
M=7, n=7, x=5 and y=5,
M=8, n=6, x=6 and y=4, or
M=5, n=7, x=5 and y=7.
In any embodiment of formula Ia described in first aspect present invention or formula Ib compound, wherein this formula Ia or formula Ib compound do not comprise 1-hexyl-2-octyl group-3,4-bis-(7-isocyanic ester heptyl)-hexanaphthene.
In an embodiment of formula Ia described in first aspect present invention or formula Ib compound, wherein this formula Ia or formula Ib compound are selected from:
1-amyl group-2-heptyl-3,4-bis-(8-isocyanic ester octyl group)-hexanaphthene,
1-hexyl-3-octyl group-2,4-bis-(7-isocyanic ester heptyl)-hexanaphthene,
1,2-diamyl-3-(10-isocyanic ester decyl)-4-(8-isocyanic ester octyl group) hexanaphthene, and
1-amyl group-3-heptyl-2,4-bis-(8-isocyanic ester octyl group)-hexanaphthene.
In an embodiment of formula Ia described in first aspect present invention or formula Ib compound, wherein this formula Ia or formula Ib compound are selected from:
1-amyl group-2-heptyl-3,4-bis-(8-isocyanic ester octyl group)-hexanaphthene.
Second aspect present invention relates to the preparation method of formula Ia described in first aspect present invention any one or formula Ib compound, and it comprises the following steps:
I) make the dimeracid compound with following formula Ia-1 or formula Ib-1:
Through shortening, obtain the saturated dimeracid of following corresponding formula Ia-2 or formula Ib-2:
Ii) making step I) the saturated dimeracid of gained formula Ia-2 or formula Ib-2 reacts the acyl chlorides compound that obtains following corresponding formula Ia-3 or formula Ib-3 with acyl chlorinating agent:
Iii) make step I i) gained formula Ia-3 or the acyl chlorides compound of formula Ib-3 and the trinitride that reaction of sodium azide obtains following corresponding formula Ia-4 or formula Ib-4:
Iv) making step I ii) trinitride of gained formula Ia-4 or formula Ib-4 decomposes formula Ia or the formula Ib compound obtaining described in first aspect present invention any one through isomerization,
In formula Ia-1, Ia-2, Ia-3, Ia-4 and formula Ib-1, Ib-2, Ib-3, Ib-4, one in p and q is 0, and another is 1;
M and y are 0 to 12 integer independently of one another, and m+y=12;
N and x are 0 to 12 integer independently of one another, and n+x=12.
According to the preparation method of second aspect present invention, specifically, it comprises makes dimeracid obtain saturated dimeracid through shortening, then in this solvent, obtain dimeracid acyl chlorides with acyl chlorinating agent again, then again with reaction of sodium azide, the trinitride generating resolves into finished product through isomerization, it is characterized in that:
1. in the first step, in inert organic solvents, in room temperature～280 ℃, preferably 150～200 ℃ change into saturated dimeracid by noble metal catalyst catalytic hydrogenation;
2. in second step, by the saturated dimeracid 1. obtaining, through dehydration, still, in inert organic solvents, with 1 to 10 mole, preferably 1.05～2.2 moles of acyl chlorinating agent reactions, generate corresponding acyl chlorides;
3. in the 3rd step, by the product 2. obtaining, still in inert organic solvents, reacted at 10～150 ℃ with 2～2.5 moles of sodiumazide, generate corresponding trinitride;
4. in the 4th step, still in inert organic solvents, heat 30～150 ℃ of isomerization decomposition and inversion become thick product by the product 3. obtaining, thick product obtains finished product through the preferred molecular distillation of vacuum distilling.
In the preparation method's of second aspect present invention a embodiment, it is characterized in that selected solvent is aliphatic hydrocarbon, aromatic hydrocarbons, alkane aromatic hydrocarbons or its chloro thing, for example benzene,toluene,xylene, trimethylbenzene, durene, heptane, octane, sherwood oil, industrial naptha, or their part mixture.In the preparation method's of second aspect present invention a embodiment, it is characterized in that, four steps can be used identical or different solvent, can in same solvent, carry out whole four-step reactions, or in different steps, use respectively different solvents or a part of step to use a kind of solvent and another part step is used another kind of solvent.In the preparation method's of second aspect present invention a embodiment, it is characterized in that hydrogenation catalyst used is noble metal catalyst, preferably palladium catalyst.In the preparation method's of second aspect present invention a embodiment, it is characterized in that acyl chlorinating agent used is sulfur oxychloride, oxalyl chloride, phosphorus trichloride, silicon tetrachloride, higher boil organic acid acyl chlorides, consumption is 1-10 mole.Preferred 1.05-2.5 mole.In the preparation method's of second aspect present invention a embodiment, it is characterized in that the first-selected sulfur oxychloride of acyl chlorinating agent, the consumption of sulfur oxychloride is 2～10 moles, preferably 2.05～2.2 moles.In the preparation method's of second aspect present invention a embodiment, the consumption that it is characterized in that sodiumazide is 2～2.5 moles, preferably 2.05～2.2 moles.In the preparation method's of second aspect present invention a embodiment, it is characterized in that the temperature of reaction of shortening is in room temperature～280 ℃, preferably 150～200 ℃.In the preparation method's of second aspect present invention a embodiment, it is characterized in that the temperature of acyl chloride reaction is at-20 ℃～100 ℃, preferably 60 ℃～80 ℃.In the preparation method's of second aspect present invention a embodiment, it is characterized in that the temperature of azido reaction is at 10～150 ℃, preferably 10～140 ℃.In the preparation method's of second aspect present invention a embodiment, it is characterized in that temperature that isomerization decomposes is at 30～150 ℃, preferably 30～140 ℃.In the preparation method's of second aspect present invention a embodiment, it is characterized in that every step inert solvent used can be different, can be identical, preferably identical, preferably toluene, dimethylbenzene or trimethylbenzene or boiling point are at the solvent of 100～180 ℃.In the preparation method's of second aspect present invention a embodiment, it is characterized in that purifying products method used is vacuum distilling, preferably molecular distillation.
In the preparation method's of second aspect present invention a embodiment, this formula Ia or formula Ib compound do not comprise 1-hexyl-2-octyl group-3,4-bis-(7-isocyanic ester heptyl)-hexanaphthene.
Third aspect present invention relate to described in first aspect present invention any one formula Ia or formula Ib compound as a kind of component the purposes in producing polyurethane lacquer, coating, elastomerics, tackiness agent, textile finshing agent or rocket propellant.
In an embodiment of third aspect present invention, relate to described in first aspect present invention any one formula Ia or formula Ib compound as a kind of component the purposes in producing polyurethane lacquer, coating, elastomerics, tackiness agent or textile finshing agent.
Detailed Description Of The Invention:
First aspect present invention provides formula Ia or formula Ib compound, and for clarity, cyclohexane ring is wherein to connect substituting group-(CH
2)
y-CH
3ring carbon atom be 1-position, six ring carbon atoms are by serial number shown below:
" (the CH occurring in the compound of formula Ia of the present invention or formula Ib
2-CH
2)
p-" or " (CH
2-CH
2)
q-", p wherein and q be 0 or 1 and p not identical with q,, when p or q are 0, they represent a key, when p or q are 1, they represent an ethylidene linking group.In addition, in the compound of formula Ia-1 of the present invention or formula Ib-1, occur " (CH=CH)
p-" or " (CH=CH)
q-", p wherein and q be 0 or 1 and p not identical with q,, when p or q are 0, they represent a key, when p or q are 1, they represent the vinyl linking group of a divalence.
The method of preparing formula Ia of the present invention or formula Ib compound can be: (the dimeracid compounds shown in through type Ia-1 or formula Ib-1 obtains saturated dimeracid through shortening, the saturated dimeracid that two keys on six-ring are obtained with replacing the equal hydrogenation of two keys on chain hydrocarbon), then make the saturated dimeracid of gained react and obtain corresponding acyl chlorides with acyl chlorinating agent (as sulfur oxychloride), and then make this acyl chlorides and reaction of sodium azide obtain corresponding trinitride, then divide and solve target product through isomerization.
In a special embodiment of second aspect present invention, a kind of method of preparing formula Ia of the present invention or formula Ib aliphatic isocyanates is provided, particularly preparation is 1-amyl group-2-heptyl-3,-hexanaphthene (for 4-bis-(8-isocyanic ester octyl group), PRO1401) method, the method comprises that with dimeracid compound shown in following A, B, C or D be raw material:
A：
Wherein m, n, x, y are 0-12 integer, m+y=12, n+x=12; Representative substances has: (m=8, n=6, x=6, y=4), (m=7, n=5, x=7, y=5), (m=8, n=8, x=4, y=4) and (m=5, n=5, x=7, y=7),
B：
Wherein m, n, x, y are 0-12 integer, m+y=12, n+x=12; Representative substances has: (m=8, n=8, x=4, y=4), (m=7, n=7, x=5, y=5), (m=8, n=6, x=6, y=4) and (m=5, n=7, x=5, y=7),
C：
Wherein m, n, x, y are 0-12 integer, m+y=12, n+x=12.Representative substances has: (m=8, n=6, x=6, y=4), (m=7, n=5, x=7, y=5), (m=8, n=8, x=4, y=4) and (m=5, n=5, x=7, y=7),
D：
Wherein m, n, x, y are 0-12 integer, m+y=12, n+x=12; Representative substances has: (m=8, n=8, x=4, y=4), (m=7, n=7, x=5, y=5), (m=8, n=6, x=6, y=4) and (m=5, n=7, x=5, y=7).
Above-mentioned dimeracid compound is obtained to saturated dimeracid through shortening, then as sulfur oxychloride reacts, obtain corresponding acyl chlorides with acyl chlorinating agent, and then obtain corresponding trinitride with reaction of sodium azide, then divide and solve target product through isomerization.
In an embodiment of second aspect present invention, can in same solvent, complete hydrogenation, chloride, azide, isomerization four-step reaction.
In an embodiment of second aspect present invention, the method comprises: 1. from dimeracid, through shortening, obtain saturated dimeracid, 2. then chloride in same solvent, 3. follows azide in same solvent again, 4. re-isomerization becomes isocyanic ester, it is characterized in that:
1. in the first step, at the temperature of room temperature to 280 ℃, the dimeracid compounds catalytic hydrogenation by shown in formula Ia-1 or formula Ib-1, obtains the saturated dimeracid shown in formula Ia-2 or formula Ib-2;
2. in second step, make to be reacted with acyl chlorinating agent in same solvent by the saturated dimeracid shown in the formula Ia-2 1. obtaining or formula Ib-2, generate the acyl chlorides shown in corresponding formula Ia-3 or formula Ib-3;
3. in the 3rd step, make by the acyl chlorides shown in the formula Ia-3 2. obtaining or formula Ib-3 in same solvent with reaction of sodium azide, generate the trinitride shown in corresponding formula Ia-4 or formula Ib-4;
4. in the 4th step, make to carry out isomerization decomposition by the trinitride shown in the formula Ia-4 3. obtaining or formula Ib-4 (this trinitride can directly be used without separation), generate thick product (being the isocyanate compound shown in formula Ia or formula Ib), then obtain finished product through decompression molecular distillation.
In the present invention, 1. above-mentioned steps can carry out by following approach: the dimeracid mixture of dimeracid (or containing) is added in withstand voltage reactor, then adds catalyzer and inert solvent, at the temperature of room temperature to 280 ℃, reaction 4-20 hour, hydrogen pressure is 0.1 to 3.0MPa, and preferred condition is 150～210 ℃ of temperature, pressure 1.5～2.5MPa, time 4-10 hour, most preferred condition is 180～200 ℃ of temperature, pressure 1.8～2.2MPa, 6～8 hours time.
Step 1. inert solvent used can be to the good inert solvent of dimeracid solvability, this solvent can not with acyl chlorinating agent, reaction of sodium azide, available solvent can be aliphatic hydrocarbon, aromatic hydrocarbons or alkane aromatic hydrocarbons.The example of these solvents is: pentane, hexane, heptane, octane, decane, dodecane and senior straight or branched aliphatic hydrocarbon and its mixture, as petroleum naphtha or sherwood oil, benzene,toluene,xylene, trimethylbenzene, durene, ethylbenzene, diethylbenzene, also can use their mixture, preferred solvent is dimethylbenzene, trimethylbenzene or the boiling point above-mentioned solvent between 100 ℃-180 ℃.
Step 1. used catalyst is the platinum metals being loaded on suitable carrier, for example palladium, platinum, rhodium or ruthenium, preferably palladium or platinum.Suitable carrier is gac, SiO
2, Al
2o
3with other carrier.Most preferably use palladium/activated-carbon catalyst.In raw material, the usage quantity of platinum metals/carried catalyst be platinum metals 0.1 to 10wt%, preferred 1～2wt%.
The mixture that 1. step obtains after filtration, dry after, can be directly used in next step reaction.
Step of the present invention 2. in, the product that 1. step obtains can directly be used, solvent can be constant, can be by 1～10 molar weight (with respect to the step of 1 molar weight 1. for products therefrom, similarly explain to have with this in this article and locate identical implication, acyl chlorinating agent except as otherwise noted) and step 1. products therefrom are reacted, and step 2. selected acyl chlorinating agent can be sulfur oxychloride, oxalyl chloride, phosphorus trichloride, silicon tetrachloride, higher boil organic acid acyl chlorides etc.Step temperature of reaction 2. can be-20 ℃ to 90 ℃, and the time can be 2-10 hour.Preferably, the amount of acyl chlorinating agent can be 1.05～5 molar weights, and temperature can be 0～80 ℃, and the time can be 6～8 hours.
Step of the present invention 3. in, the product that 2. step can be obtained removes excessive acyl chlorinating agent, then can be directly with 2～3 molar weights (with respect to the step of 1 molar weight 2. for products therefrom, similarly explain to have with this in this article and locate identical implication, reaction of sodium azide except as otherwise noted), solvent can be constant, and temperature can be 10-150 ℃, and the time can be 1～24 hour.Preferably, the amount of sodiumazide can be 2.1～2.4 molar weights, and temperature can be 10～140 ℃, and the time can be 10～16 hours.
Step of the present invention 4. in, the product that 3. step can be obtained removes after sodium-chlor, direct heating, until without γ-ray emission.The temperature of reaction can be 30～150 ℃, preferably 30～140 ℃; The time of reaction can be 5～80 hours, preferably 10～50 hours.After gained mixture desolvation, then underpressure distillation, preferably use molecular distillation, obtain formula Ia of the present invention or formula Ib compound.
Inert solvent in above-mentioned each step reaction can be identical, also can be different; In one embodiment, the solvent phase using in described each step above is same.
In the preparation method's of second aspect present invention a embodiment, adopt following steps: in hydrogenation autoclave, add dimethylbenzene, add again Pd (5%)/activated-carbon catalyst, add dimeracid, in mixture, the concentration of dimeracid counts 10～50% with solvent total amount, and the weight ratio of dimeracid and palladium is 99: 1, be heated to 150～200 ℃, 1.5～2.0MPa reaction 6 hours, after hydrogenation has absorbed, cooling, stop stirring, filtering catalyst, applies mechanically, and reaction mixture is dry.
Can in the above-mentioned reaction mixture being dried, add acyl chlorinating agent more than 1.05mol, at 20-70 ℃, reaction 6-8 hour, steams unreacted acyl chlorinating agent.
Can to the above-mentioned reaction mixture that removes acyl chlorinating agent, add the sodiumazide of 2.2 moles, at 80 ℃, react 16 hours, leach the sodium-chlor of generation.
The above-mentioned reaction mixture that removes sodium-chlor can be heated to 140 ℃, until produce without nitrogen gas.
Above-mentioned reaction mixture desolvation under reduced pressure can be distilled to obtain to finished product of the present invention.
From implementation process of the present invention, can find out, in the link of whole four steps, all can use same solvent, this is the advantage that this technique is the most outstanding, highly beneficial to industrialization, and whole process operation is fairly simple, and condition is relatively gentle.
In the preparation method's of second aspect present invention a embodiment, each reactions steps can be carried out discontinuously, also can carry out continuously.
The formula Ia producing according to the inventive method or formula Ib compound particularly PRO1401 can be used as the important component of producing various auxiliary agents.For this reason, the present invention provide on the other hand formula Ia of the present invention or formula Ib compound particularly PRO1401 for the production of polyurethane lacquer, coating, elastomerics, tackiness agent, organize the purposes of finishing composition and rocket propellant.Specifically, formula Ia of the present invention or formula Ib compound be PRO1401 particularly, and they can be used as the polyurethane paint main component of varnish, can make varnish have good resistance to deterioration, as the not yellowing of paint film generating; Or they can act on tackiness agent crosslinking component, can make tackiness agent there is good water-repellancy.
Embodiment
Below by concrete intermediate and embodiment, further illustrate the present invention, still, should be understood to, these intermediates and embodiment are only used for the use specifically describing more in detail, and should not be construed as for limiting in any form the present invention.
The present invention carries out generality and/or concrete description to the material and the test method that use in test.Although be well known in the art for realizing many materials and the working method that the object of the invention used, the present invention still does to describe in detail as far as possible at this.It will be apparent to those skilled in the art that hereinafter, if not specified, material therefor of the present invention and working method are well known in the art.Especially, the initial substance formula Ia-1 that the present invention is used or the dimeracid of Ib-1 are to be reacted and made by Diels-Alder with the 18 carbon carboxylic acids containing two two keys, and they all can obtain by commercial sources.
embodiment 1,1-amyl group-2-heptyl-3, the preparation of 4-bis-(8-isocyanic ester octyl group)-hexanaphthene
Raw material: dimeracid is the dimeracid of structure below:
step 1:350g dimethylbenzene and 30g Pd (5%)/activated-carbon catalyst is (moistening: dry weight 15g, 0.45g Pd) suspension is put into 2 liters of hydrogenation autoclave, add again 320g dimeracid (98%), vacuumize respectively, nitrogen replacement, hydrogen exchange.Reaction mixture is in 170～190 ℃, and under 1.5～2.0Mp, stir about is 7.5 hours, until absorption of hydrogen is complete, stops stirring.By nitrogen pressure, leach material, catalyzer is stayed in strainer.With 350g dimethylbenzene, catalyzer counterflush is entered to reactor, add again 320g dimeracid, repeat hydrogenation, catalyst activity does not reduce, and with identical method, carries out successively 5 hydrogenation, and catalyzer is reused 4 times, by the reaction mixture thermal dehydration obtaining, obtain saturated dimeracid anhydrous solution (water white), the transformation efficiency of this step reaction is greater than 99%, gives over to lower step and uses.
step 2:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 1, at 40 ℃, slowly drip below 147.75g (2.5 molar weight) sulfur oxychloride, add rear stirring at room 2 hours, and then reflux 4 hours.Changing reflux is water distilling apparatus, steams HCl remaining in excessive sulfur oxychloride and reaction mixture.Obtain saturated dimeracid acyl chlorides.The transformation efficiency of this step reaction is greater than 95%, and reaction mixture stays does lower step use.
step 3:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 2, at room temperature from solid feed inlet, add 81.25g (2.5 molar weight) sodiumazide, then be slowly heated to 60 ℃, maintain this temperature 10 hours.The sodium-chlor generating is filtered in cooling, obtains saturated dimeracid triazo-compound.This step reaction conversion ratio is greater than 95%, and reaction solution gives over to lower step and uses.
step 4:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, add wherein saturated dimeracid triazo-compound, be heated to 120～140 ℃, till no longer emitting to gas, by this reaction mixture desolvation, and then decompression molecular distillation obtains target product 1-amyl group-2-heptyl-3,4-bis-(8-isocyanic ester octyl group)-hexanaphthene.Total recovery 95% (in starting raw material dimeracid), isocyanate content 14.0%, chloride content is less than 0.03%.
The part detail of target product is as follows:
Molecular formula: C
36h
66n
2o
2
Molecular weight: 559
Outward appearance: light yellow oily liquid.The color that it is pointed out that the formula Ia that the present invention relates to and Ib compound is more shallow, and quality is better, and for example end product is light yellow oil, and its quality is better than brown.
NCO content: 13.6-14.3%
Viscosity is at 25 ℃: 130cps
Structural formula:
The infrared measurement data of target product are as follows:
IR (kBr) γ (cm
-1): 2854.1,2924.6 (CH
2,-CH
3c-H stretching vibration);
1460.6,1355.6 (C-CH
3, C-H formation vibration);
724.1-(CH
2)
4skeletal vibration;
2269.0N=C=O isocyanic ester.
embodiment 2,1-amyl group-2-heptyl-3, the preparation of 4-bis-(8-isocyanic ester octyl group)-hexanaphthene
By being similar to embodiment 1 method, the just reaction of combination step 3,4, add after sodiumazide, temperature is increased to more than 120 ℃, the triazo-compound that the middle sodium-chlor that does not filter generation generates directly resolves into product to gas no longer emit till, then filter sodium-chlor, desolvation, then the molecular distillation that reduces pressure obtains target product.Total recovery 90% (in starting raw material dimeracid), isocyano-content 14.1%, chloride content 0.02%.
embodiment 3,1-amyl group-2-heptyl-3, the preparation of 4-bis-(8-isocyanic ester octyl group)-hexanaphthene
By being similar to embodiment 1 method, just, in the reaction of step 2, with 158.7g (1.25mol) oxalyl chloride, replace sulfur oxychloride, other condition is constant, finally with decompression molecular distillation, obtains target product.Total recovery 93% (in starting raw material dimeracid), isocyano-content 14.0%, chloride content 0.02%.
embodiment 4,1-amyl group-2-heptyl-3, the preparation of 4-bis-(8-isocyanic ester octyl group)-hexanaphthene
Raw material: dimeracid is the dimeracid of structure below:
step 1:350g dimethylbenzene and 30g Pd (5%)/activated-carbon catalyst is (moistening: dry weight 15g, 0.45g Pd) suspension is put into 2 liters of hydrogenation autoclave, add again 320g dimeracid (98%), vacuumize respectively, nitrogen replacement, hydrogen exchange.Reaction mixture is in 170～190 ℃, and under 1.5～2.0Mp, stir about is 7.5 hours, until absorption of hydrogen is complete, stops stirring.By nitrogen pressure, leach material, catalyzer is stayed in strainer.With 350g dimethylbenzene, catalyzer counterflush is entered to reactor, add again 320g dimeracid, repeat hydrogenation, catalyst activity does not reduce, and with identical method, carries out successively 5 hydrogenation, and catalyzer is reused 4 times, by the reaction mixture thermal dehydration obtaining, obtain saturated dimeracid anhydrous solution (water white), transformation efficiency is greater than 99%, gives over to lower step and uses.
step 2:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 1, at 40 ℃, slowly drip below 147.75g (2.5 molar weight) sulfur oxychloride, add rear stirring at room 2 hours, and then reflux 4 hours.Changing reflux is water distilling apparatus, steams HCl remaining in excessive sulfur oxychloride and reaction mixture.Obtain saturated dimeracid acyl chlorides, transformation efficiency is greater than 98%, and reaction mixture stays does lower step use.
step 3:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 2, at room temperature from solid feed inlet, add 81.25g (2.5 molar weight) sodiumazide, then be slowly heated to 60 ℃, maintain this temperature 10 hours.The sodium-chlor generating is filtered in cooling, obtains saturated dimeracid triazo-compound.Transformation efficiency is greater than 98%, and reaction solution gives over to lower step and uses.
step 4:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, add wherein saturated dimeracid triazo-compound, be heated to 120～140 ℃, till no longer emitting to gas, by this reaction mixture desolvation, and then decompression molecular distillation obtains target product 1-amyl group-2-heptyl-3,4-bis-(8-isocyanic ester octyl group)-hexanaphthene.Total recovery 89% (in starting raw material dimeracid), isocyano-content 13.9%, total chlorine 0.02%.
Molecular formula: C
36h
66n
2o
2
Molecular weight: 559
Outward appearance: light yellow oily liquid
NCO content: 13.6-14.3%
Viscosity is at 25 ℃: 130cps
Structural formula:
Infrared measurement data are as follows:
IR (kBr) γ (cm
-1): 2854.1,2924.6 (CH
2,-CH
3c-H stretching vibration);
1460.6,1355.6 (C-CH
3, C-H formation vibration);
724.1-(CH
2)
4skeletal vibration;
2269.0N=C=O isocyanic ester.
embodiment 5,1,2-diamyl-3-(10-isocyanic ester decyl)-4-(8-isocyanic ester octyl group) hexamethylene
the preparation of alkane
Raw material: dimeracid is the dimeracid of structure below:
step 1:350g dimethylbenzene and 30g Pd (5%)/activated-carbon catalyst is (moistening: dry weight 15g, 0.45g Pd) suspension is put into 2 liters of hydrogenation autoclave, add again 320g dimeracid (98%), vacuumize respectively, nitrogen replacement, hydrogen exchange.Reaction mixture is in 170～190 ℃, and under 1.5～2.0Mp, stir about is 7.5 hours, until absorption of hydrogen is complete, stops stirring.By nitrogen pressure, leach material, catalyzer is stayed in strainer.With 350g dimethylbenzene, catalyzer counterflush is entered to reactor, add again 320g dimeracid, repeat hydrogenation, catalyst activity does not reduce, and with identical method, carries out successively 5 hydrogenation, and catalyzer is reused 4 times, by the reaction mixture thermal dehydration obtaining, obtain saturated dimeracid anhydrous solution (water white), transformation efficiency is greater than 99%, gives over to lower step and uses.
step 2:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 1, at 40 ℃, slowly drip below 147.75g (2.5 molar weight) sulfur oxychloride, add rear stirring at room 2 hours, and then reflux 4 hours.Changing reflux is water distilling apparatus, steams HCl remaining in excessive sulfur oxychloride and reaction mixture.Obtain saturated dimeracid acyl chlorides, transformation efficiency is greater than 98%, and reaction mixture stays does lower step use.
step 3:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 2, at room temperature from solid feed inlet, add 81.25g (2.5 molar weight) sodiumazide, then be slowly heated to 60 ℃, maintain this temperature 10 hours.The sodium-chlor generating is filtered in cooling, obtains saturated dimeracid triazo-compound.Transformation efficiency is greater than 98%, and reaction solution gives over to lower step and uses.
step 4:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, add wherein saturated dimeracid triazo-compound, be heated to 120～140 ℃, till no longer emitting to gas, by this reaction mixture desolvation, and then decompression molecular distillation obtains target product 1,2-diamyl-3-(10-isocyanic ester decyl)-4-(8-isocyanic ester octyl group) hexanaphthene.Total recovery is greater than 95% (in starting raw material dimeracid), isocyano-content 13.9%, chloride content 0.03%.
Molecular formula: C
36h
66n
2o
2
Molecular weight: 559
Outward appearance: light yellow oily liquid
NCO content: 13.6-14.3%
Viscosity is at 25 ℃: 130cps
Structural formula:
Infrared measurement data are as follows:
IR (kBr) γ (cm
-1): 2854.1,2924.6 (CH
2,-CH
3c-H stretching vibration);
1460.6,1355.6 (C-CH
3, C-H formation vibration);
724.1-(CH
2)
4skeletal vibration;
2269.0N=C=O isocyanic ester.
embodiment 6,1-amyl group-3-heptyl-2, the preparation of 4-bis-(8-isocyanic ester octyl group)-hexanaphthene
Raw material: dimeracid is the dimeracid of structure below:
step 1:
350g dimethylbenzene and 30g Pd (5%)/activated-carbon catalyst is (moistening: dry weight 15g, 0.45g Pd) suspension is put into 2 liters of hydrogenation autoclave, add again 320g dimeracid (98%), vacuumize respectively, nitrogen replacement, hydrogen exchange.Reaction mixture is in 170～190 ℃, and under 1.5～2.0Mp, stir about is 7.5 hours, until absorption of hydrogen is complete, stops stirring.By nitrogen pressure, leach material, catalyzer is stayed in strainer.With 350g dimethylbenzene, catalyzer counterflush is entered to reactor, add again 320g dimeracid, repeat hydrogenation, catalyst activity does not reduce, and with identical method, carries out successively 5 hydrogenation, and catalyzer is reused 4 times, by the reaction mixture thermal dehydration obtaining, obtain saturated dimeracid anhydrous solution (water white), transformation efficiency is greater than 99%, gives over to lower step and uses.
step 2:
Many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 1, at 40 ℃, slowly drip below 147.75g (2.5 molar weight) sulfur oxychloride, add rear stirring at room 2 hours, and then reflux 4 hours.Changing reflux is water distilling apparatus, steams HCl remaining in excessive sulfur oxychloride and reaction mixture.Obtain saturated dimeracid acyl chlorides, transformation efficiency is greater than 95%, and reaction mixture stays does lower step use.
step 3:
Many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 2, at room temperature from solid feed inlet, add 81.25g (2.5 molar weight) sodiumazide, then be slowly heated to 60 ℃, maintain this temperature 10 hours.The sodium-chlor generating is filtered in cooling, obtains saturated dimeracid triazo-compound.Transformation efficiency is greater than 98%, and reaction solution gives over to lower step and uses.
step 4:
Many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, add wherein saturated dimeracid triazo-compound, be heated to 120～140 ℃, till no longer emitting to gas, by this reaction mixture desolvation, and then decompression molecular distillation obtains target product 1-amyl group-3-heptyl-2,4-bis-(8-isocyanic ester octyl group)-hexanaphthene.Total recovery 90% (in starting raw material dimeracid), isocyano-content 14.0%, chloride content 0.03%.
Molecular formula: C
36h
66n
2o
2
Molecular weight: 559
Outward appearance: light yellow oily liquid
NCO content: 13.6-14.3%
Viscosity is at 25 ℃: 130cps
Structural formula:
Infrared measurement data are as follows:
IR (kBr) γ (cm
-1): 2854.1,2924.6 (CH
2,-CH
3c-H stretching vibration);
1460.6,1355.6 (C-CH
3, C-H formation vibration);
724.1-(CH
2)
4skeletal vibration;
2269.0N=C=O isocyanic ester.
embodiment 7,1-hexyl-3-octyl group-2, the preparation of 4-bis-(7-isocyanic ester heptyl)-hexanaphthene
Raw material: dimeracid is the dimeracid of structure below:
step 1:350g dimethylbenzene and 30g Pd (5%)/activated-carbon catalyst is (moistening: dry weight 15g, 0.45g Pd) suspension is put into 2 liters of hydrogenation autoclave, add again 320g dimeracid (98%), vacuumize respectively, nitrogen replacement, hydrogen exchange.Reaction mixture is in 170～190 ℃, and under 1.5～2.0Mp, stir about is 7.5 hours, until absorption of hydrogen is complete, stops stirring.By nitrogen pressure, leach material, catalyzer is stayed in strainer.With 350g dimethylbenzene, catalyzer counterflush is entered to reactor, add again 320g dimeracid, repeat hydrogenation, catalyst activity does not reduce, and with identical method, carries out successively 5 hydrogenation, and catalyzer is reused 4 times, by the reaction mixture thermal dehydration obtaining, obtain without water saturation dimeracid solution (water white), transformation efficiency is greater than 99%, gives over to lower step and uses.
step 2:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 1, at 40 ℃, slowly drip below 147.75g (2.5 molar weight) sulfur oxychloride, add rear stirring at room 2 hours, and then reflux 4 hours.Changing reflux is water distilling apparatus, steams HCl remaining in excessive sulfur oxychloride and reaction mixture.Obtain saturated dimeracid acyl chlorides, transformation efficiency is greater than 98%, and reaction mixture stays does lower step use.
step 3:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 2, at room temperature from solid feed inlet, add 81.25g (2.5 molar weight) sodiumazide, then be slowly heated to 60 ℃, maintain this temperature 10 hours.The sodium-chlor generating is filtered in cooling, obtains saturated dimeracid triazo-compound.Transformation efficiency is greater than 98%, and reaction solution gives over to lower step and uses.
step 4:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, add wherein saturated dimeracid triazo-compound, be heated to 120～140 ℃, till no longer emitting to gas, by this reaction mixture desolvation, and then decompression molecular distillation obtains target product 1-hexyl-3-octyl group-2,4-bis-(7-isocyanic ester heptyl)-hexanaphthene.Total recovery 95% (in starting raw material dimeracid), isocyano-content 14.1%, chloride content 0.03%.
Molecular formula: C
36h
66n
2o
2
Molecular weight: 559
Outward appearance: light yellow oily liquid
NCO content: 13.6-14.3%
Viscosity is at 25 ℃: 130cps
Structural formula:
Infrared measurement data are as follows:
IR (kBr) γ (cm
-1): 2854.1,2924.6 (CH
2,-CH
3c-H stretching vibration);
1460.6,1355.6 (C-CH
3, C-H formation vibration);
724.1-(CH
2)
4skeletal vibration;
2269.0N=C=O isocyanic ester.
embodiment 8,1-hexyl-2-octyl group-3, the preparation of 4-bis-(7-isocyanic ester heptyl)-hexanaphthene
Raw material: dimeracid is the dimeracid of structure below:
step 1:350g dimethylbenzene and 30g Pd (5%)/activated-carbon catalyst is (moistening: dry weight 15g, 0.45g Pd) suspension is put into 2 liters of hydrogenation autoclave, add again 320g dimeracid (98%), vacuumize respectively, nitrogen replacement, hydrogen exchange.Reaction mixture is in 170～190 ℃, and under 1.5～2.0Mp, stir about is 7.5 hours, until absorption of hydrogen is complete, stops stirring.By nitrogen pressure, leach material, catalyzer is stayed in strainer.With 350g dimethylbenzene, catalyzer counterflush is entered to reactor, add again 320g dimeracid, repeat hydrogenation, catalyst activity does not reduce, and with identical method, carries out successively 5 hydrogenation, and catalyzer is reused 4 times, by the reaction mixture thermal dehydration obtaining, obtain saturated dimeracid anhydrous solution (water white), transformation efficiency is greater than 99%, gives over to lower step and uses.
step 2:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 1, at 40 ℃, slowly drip below 147.75g (2.5 molar weight) sulfur oxychloride, add rear stirring at room 2 hours, and then reflux 4 hours.Changing reflux is water distilling apparatus, steams HCl remaining in excessive sulfur oxychloride and reaction mixture.Obtain saturated dimeracid acyl chlorides, transformation efficiency is greater than 95%, and reaction mixture stays does lower step use.
step 3:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, adds wherein the product of step 2, at room temperature from solid feed inlet, add 81.25g (2.5 molar weight) sodiumazide, then be slowly heated to 60 ℃, maintain this temperature 10 hours.The sodium-chlor generating is filtered in cooling, obtains saturated dimeracid triazo-compound.Transformation efficiency is greater than 98%, and reaction solution gives over to lower step and uses.
step 4:many necks bottle that agitator is housed, plug-in type thermometer is housed and with the reflux exchanger of drying tube, add wherein saturated dimeracid triazo-compound, be heated to 120～140 ℃, till no longer emitting to gas, by this reaction mixture desolvation, and then decompression molecular distillation obtains target product 1-hexyl-2-octyl group-3,4-bis-(7-isocyanic ester heptyl)-hexanaphthene.Total recovery 90% (in starting raw material dimeracid), isocyano-content 13.8%, chloride content is greater than 0.5%.
Molecular formula: C
36h
66n
2o
2
Molecular weight: 559
Outward appearance: brown oily liquids
NCO content: 13.6-14.3%
Viscosity is at 25 ℃: 130cps
Structural formula:
Infrared measurement data are as follows:
IR (kBr) γ (cm
-1): 2854.1,2924.6 (CH
2,-CH
3c-H stretching vibration);
1460.6,1355.6 (C-CH
3, C-H formation vibration);
724.1-(CH
2)
4skeletal vibration;
2269.0N=C=O isocyanic ester.
embodiment 9, comprise 1-amyl group-2-heptyl-3,4-bis-(8-isocyanic ester octyl group)-hexanaphthene
(PRO1401) lacquer formulation and preparation method thereof
In the four-hole boiling flask of 2000ml belt stirrer, reflux exchanger, water trap, thermometer, add T-20 type macromolecule polyol [viscosity 200-500 (mPa.s/25 ℃); Hydroxyl value 400-420 (mg KOH/g); Acid number 0.10 (mgKOH/g)] 150g, hexanaphthene 200g, N-BUTYL ACETATE 300g, water trap is rebasing with hexanaphthene, be heated to the 80-90 ℃ of band water that refluxes to anhydrous, then 1-amyl group-2-heptyl-3 that add 350g, 4-bis-(8-isocyanic ester octyl group)-hexanaphthene, monitored reaction system-NCO content to 2.2-2.4% every 1 hour, cooling, survey solids content, regulate solids content, filter to obtain the as clear as crystal varnish of 1000g, its color (Fe-Co colorimeter)≤2, solid divides 50 ± 2%, fineness (μ m)≤10 ,-nco value 2.2%.
embodiment 10, comprise 1-amyl group-2-heptyl-3,4-bis-(8-isocyanic ester octyl group)-hexanaphthene
(PRO1401) formula of composite solid rocket propellant
With following formula, can make a kind of composite solid rocket propellant:
| HTPB [hydroxy-terminated polybutadienes, molecular weight 2000-3000, hydroxyl value 0.5 (mmol/g)] | 12 parts |
| Al(35mu) | 17 parts |
| AP (20-200mu, ammoniumper chlorate) | 69.34 parts |
| DOA (Octyl adipate) | 1 part |
| PRO1401 | 0.75 part |
| TPTC (fentin chloride) | 0.01 part |
It can the disclosed method of reference or method known to those skilled in the art prepare, the anti-environmental aging performance of this propelling agent is better than the curing propelling agent of TDI.
Claims (9)
1. compound, 1-amyl group-3-heptyl-2,4-bis-(8-isocyanic ester octyl group)-hexanaphthene.
2. the preparation method of compound described in claim 1, it comprises the following steps:
I) make the dimeracid compound with following formula Ib-1:
Through shortening, obtain the saturated dimeracid of following corresponding formula Ib-2:
Ii) making step I) the saturated dimeracid of gained formula formula Ib-2 reacts the acyl chlorides compound that obtains following corresponding formula Ib-3 with acyl chlorinating agent:
Iii) make step I i) the acyl chlorides compound of gained formula Ib-3 and the trinitride that reaction of sodium azide obtains following corresponding formula Ib-4:
Iv) making step I ii) trinitride of gained formula Ih-4 is through decomposing and obtain compound claimed in claim 1 through isomerization,
In formula Ib-1, Ib-2, Ib-3, Ib-4,
m=8，n=6，x=6，y=4，p=1，q=0。
3. the method for claim 2, it comprises from dimeracid and obtains saturated dimeracid through shortening, then chloride in same solvent, more then azide in same solvent, re-isomerization becomes isocyanic ester, wherein:
1. in the first step, at the temperature of room temperature to 280 ℃, the dimeracid compounds catalytic hydrogenation by shown in formula Ib-1, obtains the saturated dimeracid shown in formula Ib-2;
2. in second step, make to be reacted with acyl chlorinating agent in same solvent by the saturated dimeracid shown in the formula formula Ib-2 1. obtaining, generate the acyl chlorides shown in corresponding formula formula Ib-3;
3. in the 3rd step, make by the acyl chlorides shown in the formula formula Ih-3 2. obtaining in same solvent with reaction of sodium azide, generate the trinitride shown in corresponding formula formula Ib-4;
4. in the 4th step, make to carry out isomerization decomposition by the trinitride shown in the formula Ib-4 3. obtaining, generate thick product, i.e. compound claimed in claim 1, then obtain finished product through decompression molecular distillation.
4. the method for claim 3, can directly be used without separation at the trinitride described in the 4th step.
5. the method for claim 3, wherein the first step is reacted aliphatic hydrocarbon, aromatic hydrocarbons, alkane aromatic hydrocarbons or its chloro thing in being selected from following solvent, or their part mixture; And/or each step is used identical or different solvent.
6. the method for claim 3, wherein the first step is reacted in being selected from following solvent: benzene,toluene,xylene, trimethylbenzene, durene, heptane, octane, sherwood oil, industrial naptha, or their part mixture.
7. the method for claim 3, in wherein said the first step catalytic hydrogenation, used catalyst is selected from palladium, platinum, rhodium or ruthenium; And/or described second step acyl chlorinating agent used is selected from sulfur oxychloride, oxalyl chloride, phosphorus trichloride, silicon tetrachloride, higher boil organic acid acyl chlorides.
Described in claim 1 compound as a kind of component the purposes in producing coating, elastomerics, tackiness agent, textile finshing agent or rocket propellant.
Described in claim 1 compound as a kind of component the purposes in producing polyurethane lacquer.
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