CN108329222A - A method of prepare ether, alkyl diol-it is bis--P aminobenzoates - Google Patents
A method of prepare ether, alkyl diol-it is bis--P aminobenzoates Download PDFInfo
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- CN108329222A CN108329222A CN201711468328.6A CN201711468328A CN108329222A CN 108329222 A CN108329222 A CN 108329222A CN 201711468328 A CN201711468328 A CN 201711468328A CN 108329222 A CN108329222 A CN 108329222A
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- ether
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/3331—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic
- C08G65/33313—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic aromatic
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of preparing the double P aminobenzoates of ether, alkyl diol, the this technology for preparing such compound is using ether glycol or alkyl diol as the raw material of bridge formation, ester exchange reaction is carried out under the action of effective catalyst with the ester of p-aminobenzoic acid short chain, reaction is carried out by two conversion zones of low high temperature, solvent can finally obtain the light-coloured prods of high-purity using the mixed xylenes being mixed in a certain ratio, the technical process for formula for the treatment of different things alike.Content through efficient liquid phase chromatographic analysis target product reaches 99% or more , Unit esters less than 1%, and (100 DEG C/10 Torrs) of volatile matter is less than 0.2%, 220 DEG C/5 Torrs lower heat loss 0.1% hereinafter, the consumption of p-aminobenzoic acid short-chain ester close to theoretical amount.
Description
Technical field
The invention belongs to specialty chemicals and technical field of fine, it is related to that a kind of to prepare ether, alkyl diol-bis--right
The method of Aminobenzoate.Ether or alkyl diol-it is bis--P aminobenzoates are a kind of Aromatic primary diamines class compounds,
Important use value is all had in polyurethane binder, sealing material and elastomer, in epoxy resin field as solid
Agent and flexible modifying agent have good performance.
Background technology
The shaping characteristic of polyurethane and epoxy molecule determine chain extension-crosslinking agent and curing agent in its synthesis technology and
Important function in performance design, it is not only involved in the composition of molecule, and for the conformation of the soft or hard phase region of polymer, crystallinity
Can, separation tendency influence very big, in the case where large raw material determine, chain extension-crosslinking agent and curing agent are the producers according to property
The important selection of optimum efficiency can be pursued with technological requirement adjustment formula.Chain extension-crosslinking agent and the differential responses of curing agent activity,
Different functional groups structure, the new varieties of different dosage forms also usually cause the weight of polyurethane and epoxy resin composite materials technology of preparing
Big innovation.Therefore chain extension-crosslinking agent and curing agent are most important for both synthetic materials.Both at home and abroad to its new product development,
The reformed AHP of application study and synthesis technology is paid much attention to.
The compound of ether glycol (or alkyl diol)-bis--(p-aminobenzoic acid) ester, their chain extensions as polyurethane
The curing agent domestic and international application patent of crosslinking agent and epoxy resin is many, also quite a lot for its synthesis patent.It is beautiful
It is by isocyanate-terminated amino ester prepolymer that state's patent 3932360, which discloses a kind of polyurethane product vulcanized with Diamines,
With with alkyl diol-it is bis--compound of (Para-Aminobenzoic) ester structure reacts and is made.United States Patent (USP) 6114488 discloses
It is a kind of to prepare polyurethane elastomer, especially with preparation method of the rotary casting on roll centre, including by polyurethane prepolymer
The performed polymer of body, especially TDI series, amine chain extender and polyalcohol mix in mixing head, then by this mixture
In the heart coated in casting mold or rotating roller.According to this patent, include using the amine chain extender in rotary casting technique：2-
The virtue of polyalcohol that 45% p-aminobenzoic acid is modified (i.e. ether glycol-bis--(Para-Aminobenzoic) ester) and 55-98%
Fragrant race's polyamines.This patent prepares cast elastomers, and good, which is sizing material, has hardness high (at least up to Shao D50), and elongation is (extremely
It is few 200%) and the excellent comprehensive performances such as dynamic property, anti-hydrolytic performance and thermal stability are good up to.In addition, the method is made
The reactivity of vulcanizing agent is particularly suitable for relatively high to static and dynamic physical performance requirement, is used in high speed top load
, to the bonding of metal roll centre will be good idler wheel, rubber tire rotary casting.United States Patent (USP) 5183877 discloses a kind of two-component
Adhesive is to use polyureas or polyurethane/urea performed polymer to improve the bonding between plastics and metal and plastics and elastomer
Power.The formula of the two-component adhesive includes polyamines, especially polytetramethylene ether diol (the AB- of Aminobenzoate sealing end
PTMEG, i.e. ether glycol-be bis--(Para-Aminobenzoic) ester) and aromatic diamine mixture and by isocyanates and AB-
PTMEG reacts and the polyureas performed polymer of generation.
The patent in terms of synthesis is made a general survey of, the representative are several in this way, United States Patent (USP) 4283549 discloses synthesis of alkyl
Glycol-is bis--preparation method of (Para-Aminobenzoic) ester, be by nitrobenzoic acid molten state and certain glycol be esterified it is anti-
It answers, then intermediate product is dissolved in in the solvent for being slightly soluble in water (such as aromatic hydrocarbon, ether, ester), nitro is carried out with hydrogen to add hydrogen
Reduction.This solvent for being slightly soluble in water is preferably methyl phenyl ethers anisole, and remaining acid is converted to sodium salt and is removed together with water.The technique avoids
The corrosion of hydrochloric acid, still, the technics comparing is complicated in itself, needs filtering, the separation of acid and acid and methyl phenyl ethers anisole
The processes such as recycling.
1,3-PD-that United States Patent (USP) 4476318 discloses is bis--preparation method of (p-aminobenzoic acid) ester, the technique
For the alkali metal salt and dihalopropane of p-aminobenzoic acid, reacted in nonpolar solvent, it is this according to the patent introduction
The esterification technique of dibasic acid esters does not cause any undesirable side reaction, thus object 1,3-PD-it is bis--(p- aminobenzoic
Acid) ester purity and yield it is all very high.But the technique is related to a problem, that is, the processing containing used halide fluids is asked
Topic further needs exist for solving the problems, such as to detach and recycling, to increase operation rate.
1,3-PD-that Japan Patent Kokai 58059949A2 are disclosed is bis--the preparation side of (Para-Aminobenzoic) ester
Method is sylvite by Cl (CH2) 3R (R=Cl, Br) and p-aminobenzoic acid or sodium salt in a kind of nonpolar solvent (such as dimethyl
Formamide, Er Jia Ji Ya Sulfone or N methyl pyrrolidones) in heated, 1, the 3- dichloropropanes (Cl (CH2) 3Cl) of 0.15mol
It is dissolved in Er Jia Ji Ya Sulfone with the para aminobenzoic acid sodium salt of 0.3mol, is reacted 3 hours at 100 DEG C, it is 97.4% that purity, which can be obtained,
1,3-PD-it is bis--(Para-Aminobenzoic) ester, yield 91.5% makees solvent than spent glycol and is higher by 3%.But it uses
Cl (CH2) nCl (n=2,4,5,8) replaces Cl (CH2) 3Cl, obtain corresponding alkylene-it is bis--receipts of (Para-Aminobenzoic) ester
Rate is very low.
Deutsche Bundespatent OLS2902740 disclose alkyl diol-it is bis--(Para-Aminobenzoic) ester passes through nitrobenzoic acid and two
Alcohol OH (CH2) nOH (n=2,3,5,6) carries out esterification, and catalyst is a kind of aromatic sulfuric acid, then to nitro compound
Object restores to obtain product.
U.S.'s Air Products Company China's application patent CN101353311A, it is entitled《P aminobenzoates
Preparation method》, be directed to from the point of view of disclosure be also ether glycol-it is bis--preparation process of (p-aminobenzoic acid) ester, adopt
It is the method for transesterification, is first to react with ethylaminobenzoate by auxiliary alcohol such as isobutanol and generate longer carbon chain
Then P aminobenzoates carry out transesterification with ether glycol again and obtain target product, its purpose is to reduce to amino
The distillation of ethyl benzoate is lost, but that brings has been comparable to more single step reaction, also bring post-process the separation of different alcohol with
The trouble of recycling, so-called in technical background " yield that this technology does not have the volatility of aminobenzoic acid alkyl ester to bring reduces,
Reaction time grows and operational problem " it can may not effectively be realized in actual fabrication process.
Make a general survey of synthetic method described in above-mentioned patent, integrate there is a problem that it is such or such, therefore still
So there is the necessity for developing new synthetic method.
Invention content
To overcome above-mentioned deficiency in the prior art, present invention aims at provide it is a kind of prepare ether, alkyl diol-it is bis--
The method of P aminobenzoates is the p-aminophenyl first with two moles using ether glycol or alkyl diol as bridge formation compound
The ester of sour short carbon chain, in the presence of effective catalyst, using a certain proportion of mixed xylenes as solvent, be divided to two it is different
Temperature section carries out ester exchange reaction, obtains target product.
In order to achieve the above objects and other related objects, the present invention provide it is a kind of prepare ether, alkyl diol-it is bis--to amino
The method of benzoic ether, is chemically reacted as the following formula：
Wherein, in formula the R in-(RO-) n and-ORO- is the straight chain of 2-6 carbon atom or the alkyl with branch, n 3-
Integer between 30；In the presence of a catalyst, using mixed xylenes as solvent, it is divided to cold stage and hot stage two ranks
Section completes entire ester exchange reaction.
In above-mentioned technical proposal, related content is explained as follows：
1, in said program, the solvent is mixed xylenes, and the wherein content of ortho-xylene is greater than or equal to 10%, second
The content of benzene is less than or equal to 10%.Solvent for use is mixed xylenes, there are certain requirements to the ratio of each component, mainly makes
Its boiling point under normal pressure matches with the reaction temperature controlled.
2, in said program, the cold stage is that pressure of the reaction temperature in 140-145 DEG C, reaction kettle is normal pressure,
Reaction time is 2-3 hours；The hot stage is that pressure of the reaction temperature in 165-170 DEG C, reaction kettle is 0.101-
0.105MPa, reaction time are 1-2 hours.
3, in said program, ether glycol or carbon atom number that the ether glycol is molecular weight 150-1000 are 2-6's
Straight chain or alkyl diol with branch, the carbon atom number is the straight chain of 2-6 or the alkyl diol with branch includes second two
Alcohol, propylene glycol, n-butanol, isobutanol.
4, in said program, the catalyst is stannous octoate, stannous oxalate, dibutyltin dilaurate, dibutyl
Two-2-methylhexanoic acid ester of tin, tetra isopropyl titanate, tetrabutyl titanate ester or four-2- ethyl hexyl titanate esters.
5, in said program, the ester of p-aminobenzoic acid short carbon chain used is excellent with methyl p-aminobenzoate or ethyl ester
Choosing, the shorter easier progress of ester exchange reaction with build bridge ether glycol or alkyl diol used of carbochain.
6, in said program, two temperature sections is divided to be reacted, the ester and ether of this p-aminophenyl acid short carbon chain can be made
The transesterification of the bridge type of base glycol or alkyl diol carries out more thorough.Low-temperature zone after reaction reaction solution through analysis,
The content 10% of middle unreacted P aminobenzoates, the monoesters that transesterification generates are 8%.Even if low-temperature zone extends the reaction time
Amount to 5 hours, perfect condition is still not achieved in analysis result, and wherein P aminobenzoates drop to 5%, the content of monoesters
4%, then to extend the time situation almost unchanged.But it is divided to two temperature sections to carry out, response situation has greatly change, high temperature section to carry out
2.5 hour analyses, unreacted P aminobenzoates only 0.5%, monoesters 0.4%.There is a level pressure after having reacted in kettle
Power, at this moment decompression steam solvent mixed xylenes, and the used time is very short, it can be ensured that solvent and other low boilers steam as far as possible, protect
Demonstrate,prove the purity and color and luster of final products.
7, in said program, in chemical equation described above, ether glycol or alkyl diol for bridge formation can be point
Son amount is polyethylene glycol, polypropylene glycol and poly- 1,4- butanediols of 150-1000 etc. or ethylene glycol, propylene glycol, 1,4- fourths two
Alcohol, 1,3-BDO, 1,6- hexylene glycols；2,5- hexylene glycols etc.；Reactor for this patent reaction is the band of resistance to certain pressure
Have stirring, thermometer, distillation column stainless steel reactor, be heated to be heat-conducting oil heating；The recycling of the alcohol of generated low-carbon even
It is completed with the method for rectifying；When product is solid, purified treatment is using the method recrystallized.
Since above-mentioned technical proposal is used, the present invention this have the advantage that compared with prior art：
The present invention is utilized without auxiliary alcohol to improve the temperature of esterification, keeps reaction more thorough；High temperature section it is anti-
There should be certain pressure, the distillation of the ester of p-aminobenzoic acid short carbon chain can be effectively prevent, in order to avoid cause the loss of raw material；It is whole
Point low high temperature section of a reaction carries out, and reaction can be made more complete, pure to ensure that the content of monoesters in final products is no more than 1%
Degree is up to 99% or more (efficient liquid phase chromatographic analysis value)；After completion of the reaction, decompression steams solvent and a small amount of low volatilization to high temperature section
Object, speed, removing is clean, so that the time that material is subjected to high temperature is greatly shortened, to ensure that the appearance luster of product；It steams
Go out object through dividing water, rectifying that the technical grade alcohol of low-carbon of the purity up to 99% even can be obtained, the dimethylbenzene (solvent) of recycling is containing a small amount of
P-aminophenyl acid short carbon chain ester, reused when can feed intake next time after being analyzed to identify content.
Specific implementation mode
Illustrate that embodiments of the present invention, those skilled in the art can be by this explanations by particular specific embodiment below
Content disclosed by book understands other advantages and effect of the present invention easily.
It should be clear that structural formula and reaction equation etc. appended by this specification, only to coordinate the revealed content of specification,
So that those skilled in the art understands and reads, the enforceable qualifications of the present invention are not limited to, therefore do not have technology
On essential meaning, the modification of any structure, the change of proportionate relationship or the adjustment of size can be generated not influencing the present invention
The effect of and the purpose that can reach under, should all still fall in the range of disclosed technology contents obtain and can cover.
Embodiment：
A method of prepare ether, alkyl diol-it is bis--P aminobenzoates, chemically reacted as the following formula：
Wherein, in formula the R in-(RO-) n and-ORO- is the straight chain of 2-6 carbon atom or the alkyl with branch, n 3-
Integer between 30；In the presence of a catalyst, using mixed xylenes as solvent, it is divided to two stages of cold stage and hot stage
Complete entire ester exchange reaction.
The solvent is mixed xylenes, and the wherein content of ortho-xylene is greater than or equal to 10%, and the content of ethylbenzene is less than
Or it is equal to 10%.Solvent for use is mixed xylenes, be there are certain requirements to the ratio of each component, mainly makes it under normal pressure
Boiling point match with the reaction temperature controlled.
The cold stage is that pressure of the reaction temperature in 140-145 DEG C, reaction kettle is normal pressure, reaction time 2-3
Hour；It is 0.101-0.105MPa that the hot stage, which is pressure of the reaction temperature in 165-170 DEG C, reaction kettle, when reaction
Between be 1-2 hours.
The ether glycol that the ether glycol is molecular weight 150-1000 or the straight chain that carbon atom number is 2-6 carry branch
The alkyl diol of chain, the carbon atom number is the straight chain of 2-6 or alkyl diol with branch includes ethylene glycol, propylene glycol, just
Butanol, isobutanol.
The catalyst be stannous octoate, stannous oxalate, dibutyltin dilaurate, two-2-methyl of dibutyl tin oneself
Acid esters, tetra isopropyl titanate, tetrabutyl titanate ester or four -2- ethyl hexyl titanate esters.
The ester of p-aminobenzoic acid short carbon chain used is preferred with methyl p-aminobenzoate or ethyl ester, and carbochain is shorter and frame
The easier progress of ester exchange reaction of ether glycol or alkyl diol used in bridge.
It is divided to two temperature sections to be reacted, the ester and ether glycol or alkyl two of this p-aminophenyl acid short carbon chain can be made
The transesterification of the bridge type of alcohol carries out more thorough.Reaction solution is through analysis after reaction for low-temperature zone, and wherein unreacted is to amino
The content 10% of benzoic ether, the monoesters that transesterification generates are 8%.Even if low-temperature zone extends the reaction time and amounts to 5 hours, point
Perfect condition is still not achieved in analysis result, and wherein P aminobenzoates drop to 5%, and the content of monoesters is 4%, then extends the time
The situation is almost unchanged.But it is divided to two temperature sections to carry out, response situation has greatly change, high temperature section to carry out 2.5 hour analyses, not
The P aminobenzoates of reaction only 0.5%, monoesters 0.4%.There is certain pressure after having reacted in kettle, at this moment decompression steams molten
Agent mixed xylenes, used time are very short, it can be ensured that solvent and other low boilers steam as far as possible, ensure final products purity and
Color and luster.
In chemical equation described above, it is 150-1000 that ether glycol or alkyl diol for bridge formation, which can be molecular weight,
Polyethylene glycol, polypropylene glycol and poly- 1,4-butanediol etc. or ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-BDO, 1,
6- hexylene glycols；2,5- hexylene glycols etc.；Reactor for this patent reaction is resistance to certain pressure with stirring, thermometer, steaming
The stainless steel reactor of fractional distillation column, is heated to be heat-conducting oil heating；The method of the recycling rectifying of the alcohol of generated low-carbon even is completed；
When product is solid, purified treatment is using the method recrystallized.
Embodiment one：
500 grams of PTMEG (poly- 1,4- butanediols) that molecular weight is 1000 are added to stirring, thermometer, distillation column
The resistance to stainless steel reactor for having certain pressure in, be heated to be the heating of heat conduction oil lagging, adding 1200 grams has certain ratio
The mixed xylenes of example is eventually adding 167 grams and 3 grams effective catalysts of benzocainum (ethylaminobenzoate) as solvent
(tetraisopropyl titanate).It opens and stirs and begin to warm up, the condenser pipe that distillation column is connect when temperature reaches 140-145 DEG C in kettle
In begin with lasting liquid outflow, maintain the temperature, with the amount for the liquid that heating keeps steaming, after reaction 2 hours, turn down cold
The cock of condenser increases heating power and maintains the temperature when temperature is raised to 165-170 DEG C, and the reaction was continued 1.5 hours.Then
The cock for opening condenser completely continues to heat and be gradually increased suction strength, and no liquid flows out, and temperature reaches 180- in kettle
It is maintained 10-15 minutes at 185 DEG C.It is passed through nitrogen and closes vacuum and reaction kettle is cooled down, when material reaches 120 in kettle
DEG C when be filtered, obtain light amber thick liquid, dynamic viscosity at 30 DEG C is 3200mPa.s, 220 DEG C of heat loss
0.07%, efficient liquid phase chromatographic analysis product purity 99.21%, monoester content 0.65%, unreacted PTMEG 0.13%.It steams
1245 grams of the amount of the liquid gone out obtains 99% 43 grams of ethyl alcohol after separation, steams and contains about 0.2% in the dimethylbenzene after ethyl alcohol
Benzocainum.This part benzocainum of used time should be included in the inventory of benzocainum afterwards.
Embodiment two:
234 grams of 1,3- propylene glycol are added to anti-with stirring, thermometer, the resistance to stainless steel for having certain pressure of distillation column
Answer in device, be heated to be heat conduction oil lagging heating, add 1800 grams it is above-mentioned have a certain proportion of mixed xylenes as molten
Agent is eventually adding 1005 grams and 18 grams catalyst (tetraisopropyl titanate) of benzocainum (ethylaminobenzoate).Unlatching is stirred
It mixes and begins to warm up, lasting liquid flow is begun in the condenser pipe that distillation column is connect when temperature reaches 140-145 DEG C in kettle
Go out, maintain the temperature, with the amount for the liquid that heating keeps steaming, after reacting 3 hours, turns down the cock of condenser, increase heating
Power maintains the temperature when temperature is raised to 170-175 DEG C, and the reaction was continued 2.5 hours.Then examining for condenser is opened completely
Gram, continue to heat and be gradually increased suction strength, no liquid flows out, and 10-15 points are maintained when temperature reaches 190-195 DEG C in kettle
Clock.It is passed through nitrogen and closes vacuum and reaction kettle is cooled down, stop stirring and continuing cold when material reaches 135 DEG C in kettle
Kettle cover is opened when but, to room temperature, the solid material in kettle is smashed to pieces, 2050 grams of methanol is then added, material is recrystallized.
The product being recrystallized to give is white crystalline powder, and melting range is 125-128 DEG C, and efficient liquid phase chromatographic analysis purity is 99%, is received
Rate is 97%.It is also reusable to recycle dimethylbenzene.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (5)
1. it is a kind of prepare ether, alkyl diol-it is bis--methods of P aminobenzoates, it is characterised in that：It is anti-that chemistry is carried out as the following formula
It answers：
Wherein, in formula the R in-(RO-) n and-ORO- is the straight chain of 2-6 carbon atom or the alkyl with branch, n for 3-30 it
Between integer；In the presence of a catalyst, using mixed xylenes as solvent, two stages of cold stage and hot stage is divided to complete
Entire ester exchange reaction.
2. it is according to claim 1 prepare ether, alkyl diol-it is bis--methods of P aminobenzoates, it is characterised in that：
The solvent is mixed xylenes, and wherein the content of ortho-xylene is greater than or equal to 10%, and the content of ethylbenzene is less than or equal to 10%.
3. it is according to claim 1 prepare ether, alkyl diol-it is bis--methods of P aminobenzoates, it is characterised in that：
The cold stage is that pressure of the reaction temperature in 140-145 DEG C, reaction kettle is normal pressure, and the reaction time is 2-3 hours；It is described
Hot stage is that pressure of the reaction temperature in 165-170 DEG C, reaction kettle is 0.101-0.105MPa, and the reaction time is that 1-2 is small
When.
4. it is according to claim 1 prepare ether, alkyl diol-it is bis--methods of P aminobenzoates, it is characterised in that：
The ether glycol that the ether glycol is molecular weight 150-1000 or the straight chain that carbon atom number is 2-6 or the alkyl with branch
Glycol, the carbon atom number is the straight chain of 2-6 or the alkyl diol with branch includes ethylene glycol, propylene glycol, n-butanol, isobutyl
Alcohol.
5. it is according to claim 1 prepare ether, alkyl diol-it is bis--methods of P aminobenzoates, it is characterised in that：
The catalyst is stannous octoate, stannous oxalate, dibutyltin dilaurate, two-2-methylhexanoic acid ester of dibutyl tin, four
Isopropyl titanate esters, tetrabutyl titanate ester or four -2- ethyl hexyl titanate esters.
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| CN110627669A (en) * | 2019-09-30 | 2019-12-31 | 常州市阳光药业有限公司 | Preparation method of 1, 3-propylene glycol bis (4-aminobenzoic acid) ester |
| CN112029063A (en) * | 2020-09-07 | 2020-12-04 | 江苏湘园化工有限公司 | Liquid polyurethane curing agent composition and application method thereof |
| CN112831014A (en) * | 2020-12-31 | 2021-05-25 | 江苏湘园化工有限公司 | Aromatic diamine curing agent and preparation method thereof |
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| CN110627669A (en) * | 2019-09-30 | 2019-12-31 | 常州市阳光药业有限公司 | Preparation method of 1, 3-propylene glycol bis (4-aminobenzoic acid) ester |
| CN110627669B (en) * | 2019-09-30 | 2022-03-22 | 常州市阳光药业有限公司 | Preparation method of 1, 3-propylene glycol bis (4-aminobenzoic acid) ester |
| CN112029063A (en) * | 2020-09-07 | 2020-12-04 | 江苏湘园化工有限公司 | Liquid polyurethane curing agent composition and application method thereof |
| CN112029063B (en) * | 2020-09-07 | 2022-01-07 | 江苏湘园化工有限公司 | Liquid polyurethane curing agent composition and application method thereof |
| CN112831014A (en) * | 2020-12-31 | 2021-05-25 | 江苏湘园化工有限公司 | Aromatic diamine curing agent and preparation method thereof |
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Application publication date: 20180727 |