CN103214667B - Polymerization method of polytetrahydrofuran single alcohol and diol mixture - Google Patents
Polymerization method of polytetrahydrofuran single alcohol and diol mixture Download PDFInfo
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- CN103214667B CN103214667B CN201310081181.0A CN201310081181A CN103214667B CN 103214667 B CN103214667 B CN 103214667B CN 201310081181 A CN201310081181 A CN 201310081181A CN 103214667 B CN103214667 B CN 103214667B
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Abstract
The invention relates to a polytetrahydrofuran preparation and purification method using alcamines substances or single alcohol substance and water as a end-capping reagent, especially relates to a polymerization method of polytetrahydrofuran single alcohol and diol mixture. The invention employs the problem that the polytetrahydrofuran diol prepared by the fluosulfonic acid method, the acetic anhydride-perchloric acid method and the concentrated sulfuric acid method has wide distribution and high viscosity, and the product should be melted by higher temperature for usage, and if the heteropoly acid method is out of control, the gel will be appeared. The invention provides a new method which employs a certain amount of hydramine or single alcohol as the end-capping reagent to prepare polytetrahydrofuran, and uniform mixing of the polytetrahydrofuran and the polytetrahydrofuran diol prepared by the end-capping reagent water can be used as a novel raw material widely applied in the fields of spandex fiber, polyurethane elastomer, ester and ether copolymerization elastomer, petrochemical industry, spaceflight, etc.
Description
Technical field
The present invention relates to a kind of using alcamines material or mono-alcohols and water as the polytetrahydrofuran of end-capping reagent preparation and method of purification thereof, especially relate to the polymerization process of a kind of polytetrahydrofuran single methanol and diol mixture.
Background technology
Polytetrahydrofuran and multipolymer thereof are a kind of use range raw materials widely, can be used as polyurethane elastomeric fiber, TPU, all respects such as aeronautical material.
The preparation method of current industrial polytetrahydrofuran mainly contains following several:
1. fluosulfonic acid method.It mainly reflects that equation is:
, the requirement of this method to equipment is high, need be large with exotic materials and fluosulfonic acid consumption, very large to environmental influence.
2. acetic anhydride-perchloric acid method.Its principal reaction equation is:
This method is with strong acid catalyst, and corrodibility is strong, very high to the requirement of equipment, and reaction subsequent processing steps is a lot, and material consumption, energy consumption are comparatively large, the economy of influence process.
3. sulphate method.Its principal reaction equation is:
This method reaction controls very strict to temperature, the higher reaction of temperature is very violent, and easy over-temp and over-pressure produces explosion hazard.
4. clay method.The raw material of the catalyzer that this kind of method is used is halloysite, the pure aluminium silicate powder after high temperature sintering, acidifying activation treatment is made a certain size the shape such as bar, ball.Tetrahydrofuran (THF) carries out reactive polymeric through fixed-bed reactor, its shortcoming is catalyzer is natural mineral, composition is unstable, the catalyst activity made is lower, must improve polymeric reaction temperature to increase speed of reaction, but equilibrium conversion reduces, side reaction increases, thus bring a series of additional process, i.e. the dedicated process such as high temperature molecular distillation, decolouring, hydrogenation, filtration, depolymerization.
But the preparation flow of these methods above is longer, and stability and the adjustability of control are poor.
Summary of the invention
The present invention is to provide the polymerization process of a kind of polytetrahydrofuran single methanol and diol mixture, its flow process mainly solving the polymerization process of polytetrahydrofuran single methanol existing for prior art and diol mixture is longer, the stability of control and poor etc. the technical problem of adjustability.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals:
The polymerization process of a kind of polytetrahydrofuran single methanol of the present invention and diol mixture, is characterized in that described method comprises:
A. in R1 reactor, heteropolyacid catalyst is dropped into, heteropolyacid catalyst controls the 1-40% at reactor volume, add by pipeline L1 the tetrahydrofuran (THF) that water content is 0.01-1% in reactor R1, the volume controlling heteropolyacid catalyst accounts for the 10%-70% of whole reaction system, preferred 25%-50%, open agitator E1, heteropolyacid catalyst is made to become quasi-fluid in the effect of agitator, obvious organic phase and catalyzer phase is formed in reactor, and detect the water-content of organic phase, constantly pass into tetrahydrofuran (THF), regulate the water-content of organic phase at 0.3-0.8%;
B. moisture content to be regulated qualified after, add containing alkylene oxides material by pipeline L1, or alcohols material, or what the tetrahydrofuran (THF) 1-10%(1-10% herein of alcohol/amine substance refers to, tetrahydrofuran (THF) accounts for the 1-10% with material), wherein alkylene oxides water content of materials 0.1-0.3%, alcohols material water content 0.02-0.1%, alcohol/amine substance water content 0.03-0.5%, coutroi velocity, make the ratio of reactor volume and pipeline L1 flow under normal pressure at 0.5-25, reaction mass is transported to catalyst sedimentation tank V1 through piping L2 under the effect of material-handling pump P2, reaction mass is after in subsider, standing sedimentation is divided into levels, the heteropolyacid catalyst of lower floor returns reactor R1 by pipeline L3 and recycles under the effect of material-handling pump P1, the flow controlling pipeline L2 equals the flow sum of pipeline L1 and L3, the liquid level of control V1 is between 50%-95%, most suitable span of control is 75%-85%,
C. tetrahydrofuran (THF) is contained in the upper materials of V1 layering, the multipolymer of polytetrahydrofuran and tetrahydrofuran (THF) thereof, a small amount of moisture and a certain amount of heteropolyacid catalyst, above material is transported to extractive reaction still R2 by L3, add extraction agent by pipeline L4 simultaneously, after extractive reaction terminates, material in extraction kettle is just divided into the organic phase on upper strata and the catalyzer phase of lower floor, the organic phase on upper strata comprises the catalyzer of trace, a certain amount of moisture, tetrahydrofuran (THF), polytetrahydrofuran and multipolymer thereof and extraction agent, the catalyzer of lower floor comprises most catalyzer mutually, part polytetrahydrofuran and multipolymer thereof, a small amount of moisture and tetrahydrofuran (THF), catalyzer returns reactor recycle,
D. the supernatant liquid after extraction is transported to azeotropic distillation column T1 under the effect of material-handling pump P3, most extraction agent and tetrahydrofuran (THF) is removed at azeotropic distillation column, after eliminating most of extraction agent and tetrahydrofuran (THF), by remaining mass transport to luwa evaporator, after luwa evaporator, finished product polytetrahydrofuran single methanol and polytetrahydrofuran diol obtain from luwa evaporator bottom collection.
The present invention mainly prepares the polytetrahydrofuran with specified property by the ratio controlling polytetrahydrofuran single methanol and glycol in reactive polymeric thing.The polytetrahydrofuran diol distribution adopting fluosulfonic acid method, acetic anhydride-perchloric acid method and sulphate method to prepare is wide, reach more than 2.0 and viscosity is very high, it must be made to melt with comparatively high temps in use could use, the standby polytetrahydrofuran of heteropolyacid legal system is adopted to have low viscosity, the characteristic of narrowly distributing.But due to its distribution uniform, the feature such as also respond concentrated in downstream application process, controls the bad gel that just there will be, therefore need the speed of exactissima diligentia synthesis phase in use.
The present invention is mainly wayward based on polytetrahydrofuran diol resultant velocity in the use procedure of downstream, need to add the reasons such as other conditioning agents, develop a kind of use convenient, more easily control the preparation method of polytetrahydrofuran diol and the polytetrahydrofuran mono alcohol mixture synthesized.
The main chemical reactions that the present invention utilizes has following
1. water and tetrahydrofuran (THF) generate the reaction of polytetrahydrofuran diol under the effect of heteropolyacid catalyst, and following reaction occurs:
2. when there being alkylene oxides to participate in (for oxyethane), there is following reaction:
3., when polyreaction is using alcamines as end-capping reagent, its reaction is (for thanomin):
4., using mono-alcohols as end-capping reagent, its reaction is (for ethanol):
R1 reactor is the polymerization reaction kettle of belt stirrer, and temperature of reaction kettle controls at 30 ~ 80 DEG C, preferably 50
-70 DEG C; The input amount of catalyzer adds according to actual needs, can be controlled in the 1-40% of reactor volume, preferred 15-30%.
In reactor R1, add the tetrahydrofuran (THF) that water content is 0.01-1% by pipeline L1, preferred water content is the tetrahydrofuran (THF) of 0.1-0.5%.
Open agitator E1, make catalyzer become quasi-fluid in the effect of agitator, in reactor, form obvious organic phase and catalyzer phase, and detect the water-content of organic phase, constantly passing into tetrahydrofuran (THF) regulates the water-content of organic phase between 0.3-0.8%, preferred 0.4-0.6%.
As preferably, described heteropolyacid catalyst is phosphorus heteropoly tungstic acid catalyzer, Al content in heteropolyacid catalyst is 0-2ppm, Fe content is 0-3ppm, Cu content is 0-2ppm, Na content is 0-30ppm, and heteropolyacid catalyst is containing 1mol/L or less free phosphorus acid group, other metal ion except tungsten is 0-50ppm, and heteropolyacid catalyst purity is greater than 96%.
As preferably, the purity of described tetrahydrofuran (THF) is greater than 99.95%, and the purity of alcohol/amine substance is greater than 99.5%, and the purity of alkylene oxides material is greater than 99%,
As preferably, described alkylene oxides is at least one in oxyethane, propylene oxide, epoxypentane.
As preferably, described alcohol/amine substance is thanomin, at least one in α-amino isopropyl alcohol.
As preferably, described finished product polytetrahydrofuran single methanol and polytetrahydrofuran diol molecular weight are that 500-3500 is adjustable, wherein polytetrahydrofuran diol content is 5-99% adjustable, is about 5-99% with the polytetrahydrofuran content of alcohol/amine end-blocking.
As preferably, the molecular weight of described polymkeric substance is 1000 ± 50,1300 ± 50,1500 ± 50,1800 ± 50,2000 ± 50 or 3000 ± 50.
As preferably, described extraction agent is the saturated hydrocarbons containing 4-12 saturated carbon atom.
As preferably, in described azeotropic distillation column, the temperature of component distillation is 70-110 DEG C, most preferably 80-100 DEG C.
As preferably, in described luwa evaporator, wiped film vaporization temperature is 110-140 DEG C, most preferably 125-135 DEG C.
Therefore, the present invention prepares the novel method of polytetrahydrofuran using a certain amount of hydramine or single methanol as end-capping reagent, and the polytetrahydrofuran diol Homogeneous phase mixing prepared as end-capping reagent with water, can widely used a kind of novel material as fields such as spandex fibre, polyurethane elastomer, ester ether copolymer elastomer, petrochemical industry, space flight, utilize the flow process of the standby poly-polytetrahydrofuran of heteropolyacid legal system shorter, the stability of control and adjustability good.
Accompanying drawing explanation
Accompanying drawing 1 is a kind of schematic flow sheet of the present invention.
Embodiment
Below by embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.
Embodiment: a kind of polytetrahydrofuran single methanol of this example and the polymerization process of diol mixture, as shown in Figure 1, its method comprises:
A. three mouthfuls of round-bottomed flasks of a 2L are prepared, the crystal water content adding heteropolyacid in this example of heteropolyacid 350g(meeting application claims is wherein 9.5), adding the water-content of tetrahydrofuran (THF) in this example of tetrahydrofuran solution 1000ml(meeting application claims wherein lower than 0.01%).The above-mentioned round-bottomed flask that heteropolyacid catalyst and tetrahydrofuran solution are housed is placed in the water-bath of 65 DEG C, one of them excuse of round-bottomed flask connects prolong, and middle excuse connects agitator.Another one excuse clogs with suitable stopper.Then opening agitator adjusting rotary speed is 350rpm, stops stirring and leaving standstill 30min after 2 hours.Heteropolyacid in above-mentioned round-bottomed flask and tetrahydrofuran (THF) are divided into upper and lower two-phase.Upper strata is organic phase (comprising a small amount of heteropolyacid catalyst be dissolved in wherein, a small amount of polytetrahydrofuran and a small amount of moisture), and lower floor is catalyzer phase (comprising a part of tetrahydrofuran (THF), moisture); Upper organic phase is taken out, adds the tetrahydrofuran (THF) the same with the tetrahydrofuran (THF) added time initial, then open agitator and stir 2 hours, after so repeatedly taking out the organic phase on upper strata again 3 times, namely obtained the catalyst solution wanted required for the present invention;
B. above-mentioned obtained catalyst solution is joined in polymerization reactor R1, reactor R1 is furnished with reflux condensation mode system and agitator E1, and make R1 keep temperature-stable (this example is 60 DEG C), by the disposable tetrahydrofuran solution that passes in reactor of pipeline L1 (containing moisture 0.45% in this solution, containing thanomin 0.015%) about 600ml, open agitator E1, arranging rotating speed is 350rpm.And then the tetrahydrofuran (THF) controlling to enter reactor R1 (contains moisture 0.45% in this solution, containing thanomin 0.015% flow velocity) flow velocity of solution is 2ml/min.The mixture stream speed control carried by P2 by pipeline L2 is made as 3ml/min, and the Material control flow velocity carried by P1 by pipeline L3 is 1ml/min, and the corresponding flow velocity controlling pipeline P3 is 2ml/min.More than control the change that should be noted liquid level, to keep the level stability of reactor R1 and settlement separate still V1.Material is divided into two-layer in settlement separate still V1, upper strata be organic phase (comprise required for the present invention want polytetrahydrofuran single methanol, polytetrahydrofuran diol, unreacted monomer tetrahydrofuran (THF) and other minor component), lower floor is catalyzer phase (comprising most catalyzer, the polytetrahydrofuran of a part, moisture and other minor component).Catalyzer is transmitted back to reactor recycle through piping L3, and organic phase is transported in extractive reaction still R2;
C. after sedimentation completes, supernatant liquid is taken out by material mutually and be transported to extractive reaction still R2, (what add this experiment is hexane to add extraction agent from pipeline L4, be that 2:1 adds according to the mass ratio of hexane and mixture), open agitator E2, arranging rotating speed is 350rpm, stops stirring after stirring 40min.After leaving standstill 20min, the material that upper strata is clarified is taken out, be transported to next handling procedure;
D. clarification material extraction stages obtained is transported to the small-molecule substances (this Setup Experiments of component distillation temperature 105 DEG C) such as the most extraction agent of azeotropic distillation column removing and tetrahydrofuran (THF), and then transporting material to luwa evaporator E13, wiped film vaporization actuator temperature is set to 125 DEG C.The product pointed by the present invention can be obtained, i.e. the mixture of polytetrahydrofuran diol, polytetrahydrofuran single methanol after luwa evaporator.After testing, the product number-average molecular weight obtained according to this embodiment is 1486, and the molecule number content of polytetrahydrofuran furans single methanol is 1.86%, and the molecule number content of polytetrahydrofuran diol is 97.66%, and other molecule number content are 0.48%.
The foregoing is only specific embodiments of the invention, but constitutional features of the present invention is not limited thereto, any those skilled in the art is in the field of the invention, and the change done or modification are all encompassed among the scope of the claims of the present invention.
Claims (10)
1. a polymerization process for polytetrahydrofuran single methanol and diol mixture, is characterized in that described method comprises:
A. in R1 reactor, heteropolyacid is dropped into, heteropolyacid controls the 1-40% at reactor volume, add by pipeline L1 the tetrahydrofuran (THF) that water content is 0.01-1% in reactor R1, the volume controlling heteropolyacid catalyst accounts for the 10%-70% of whole reaction system, open agitator E1, heteropolyacid catalyst is made to become quasi-fluid in the effect of agitator, obvious organic phase and catalyzer phase is formed in reactor, and detect the water-content of organic phase, constantly pass into tetrahydrofuran (THF), regulate the water-content of organic phase at 0.3-0.8%;
B. moisture content to be regulated qualified after, add containing alkylene oxides material by pipeline L1, or alcohols material, or the tetrahydrofuran (THF) of alcohol/amine substance, tetrahydrofuran (THF) accounts for the 1-10% of material total mass, wherein alkylene oxides water content of materials 0.1-0.3%, alcohols material water content 0.02-0.1%, alcohol/amine substance water content 0.03-0.5%, coutroi velocity, make the ratio of reactor volume and pipeline L1 flow under normal pressure at 0.5-25, reaction mass is transported to catalyst sedimentation tank V1 through piping L2 under the effect of material-handling pump P2, reaction mass is after in subsider, standing sedimentation is divided into levels, the heteropolyacid catalyst of lower floor returns reactor R1 by pipeline L3 and recycles under the effect of material-handling pump P1, the flow controlling pipeline L2 equals the flow sum of pipeline L1 and L3, the liquid level of control V1 is between 50%-95%,
C. tetrahydrofuran (THF) is contained in the upper materials of V1 layering, the multipolymer of polytetrahydrofuran and tetrahydrofuran (THF) thereof, a small amount of moisture and a certain amount of heteropolyacid catalyst, above material is transported to extractive reaction still R2 by L3, add extraction agent by pipeline L4 simultaneously, after extractive reaction terminates, material in extraction kettle is just divided into the organic phase on upper strata and the catalyzer phase of lower floor, the organic phase on upper strata comprises the catalyzer of trace, a certain amount of moisture, tetrahydrofuran (THF), polytetrahydrofuran and multipolymer thereof and extraction agent, the catalyzer of lower floor comprises most catalyzer mutually, part polytetrahydrofuran and multipolymer thereof, a small amount of moisture and tetrahydrofuran (THF), catalyzer returns reactor recycle,
D. the supernatant liquid after extraction is transported to azeotropic distillation column T1 under the effect of material-handling pump P3, most extraction agent and tetrahydrofuran (THF) is removed at azeotropic distillation column, after eliminating most of extraction agent and tetrahydrofuran (THF), by remaining mass transport to luwa evaporator, after luwa evaporator, finished product polytetrahydrofuran single methanol and polytetrahydrofuran diol obtain from luwa evaporator bottom collection.
2. the polymerization process of polytetrahydrofuran single methanol according to claim 1 and diol mixture, it is characterized in that described heteropolyacid catalyst is phosphorus heteropoly tungstic acid catalyzer, Al content in heteropolyacid catalyst is 0-2ppm, Fe content is 0-3ppm, Cu content is 0-2ppm, Na content is 0-30ppm, and heteropolyacid catalyst is containing 1mol/L or less free phosphorus acid group, other metal ion except tungsten is 0-50ppm, and heteropolyacid catalyst purity is greater than 96%.
3. the polymerization process of polytetrahydrofuran single methanol according to claim 1 and diol mixture, it is characterized in that the purity of described tetrahydrofuran (THF) is greater than 99.95%, the purity of alcohol/amine substance is greater than 99.5%, and the purity of alkylene oxides material is greater than 99%.
4. the polymerization process of polytetrahydrofuran single methanol according to claim 1 and diol mixture, is characterized in that described alkylene oxides is at least one in oxyethane, propylene oxide, epoxypentane.
5. the polymerization process of polytetrahydrofuran single methanol according to claim 1 and diol mixture, is characterized in that described alcohol/amine substance is thanomin, at least one in α-amino isopropyl alcohol.
6. the polymerization process of polytetrahydrofuran single methanol according to claim 1 and diol mixture, it is characterized in that described finished product polytetrahydrofuran single methanol and polytetrahydrofuran diol molecular weight are that 500-3500 is adjustable, wherein polytetrahydrofuran diol content is that 5-99% is adjustable, with the polytetrahydrofuran content 5-99% of alcohol/amine end-blocking.
7. the polymerization process of polytetrahydrofuran single methanol according to claim 6 and diol mixture, is characterized in that the molecular weight of described polymkeric substance is 1000 ± 50,1300 ± 50,1500 ± 50,1800 ± 50,2000 ± 50 or 3000 ± 50.
8. the polymerization process of polytetrahydrofuran single methanol according to claim 1 and diol mixture, is characterized in that described extraction agent is the saturated hydrocarbons containing 4-12 saturated carbon atom.
9. the polymerization process of polytetrahydrofuran single methanol according to claim 1 and diol mixture, is characterized in that the temperature of component distillation in described azeotropic distillation column is 70-110 DEG C.
10. the polymerization process of polytetrahydrofuran single methanol according to claim 1 and diol mixture, is characterized in that in described luwa evaporator, wiped film vaporization temperature is 110-140 DEG C.
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| CN109851767B (en) * | 2018-12-20 | 2021-05-28 | 杭州三隆新材料有限公司 | Method for simultaneously preparing polytetramethylene ether glycol with various specifications |
| CN113087893B (en) * | 2021-03-23 | 2023-04-28 | 杭州三隆新材料有限公司 | Tetrahydrofuran copolymer and preparation method thereof |
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|---|---|---|---|---|
| CN1796436A (en) * | 2004-12-21 | 2006-07-05 | 四川大学 | Method for preparing polytetrahydrofuran |
| CN102432860A (en) * | 2011-07-21 | 2012-05-02 | 西北工业大学 | Preparation method for hydroxyl terminated polyethylene glycol-polytetrahydrofuran triblock copolyether |
| CN102604072A (en) * | 2012-03-02 | 2012-07-25 | 无锡阿科力化工有限公司 | Preparation method of polyether amine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796436A (en) * | 2004-12-21 | 2006-07-05 | 四川大学 | Method for preparing polytetrahydrofuran |
| CN102432860A (en) * | 2011-07-21 | 2012-05-02 | 西北工业大学 | Preparation method for hydroxyl terminated polyethylene glycol-polytetrahydrofuran triblock copolyether |
| CN102604072A (en) * | 2012-03-02 | 2012-07-25 | 无锡阿科力化工有限公司 | Preparation method of polyether amine |
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