CN108003028A - Multi-unsaturated carboxylic acid's ester is synthesized by starting material of 1,3- dichloroisopropanols - Google Patents

Multi-unsaturated carboxylic acid's ester is synthesized by starting material of 1,3- dichloroisopropanols Download PDF

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CN108003028A
CN108003028A CN201711440992.XA CN201711440992A CN108003028A CN 108003028 A CN108003028 A CN 108003028A CN 201711440992 A CN201711440992 A CN 201711440992A CN 108003028 A CN108003028 A CN 108003028A
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sodium
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王建华
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/604—Polycarboxylic acid esters, the acid moiety containing more than two carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters

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Abstract

With 1,3 dichloroisopropanols synthesize multi-unsaturated carboxylic acid's ester for starting material, collaboration method of 1,3 dichloroisopropanol from patent CN2017111426887 prepares the accessory substance of vinyl carboxylates product, the resin raw material that multi-unsaturated carboxylic acid's ester and vinyl carboxylates can be coating material solidified as UV.Multi-unsaturated carboxylic acid's ester includes（Formula 15）、（Formula 16）、（Formula 17）Three class formations, wherein, R1、R2Each stand alone as H or methyl；R3For OH or、、、、Or R4M, M are H or Na or K；R4For、、、、、；n≥1.The more valuable meaning of the present invention is, the present invention is combined with collaboration legal system vinyl carboxylates, preparing epoxy chloropropane by using glycerol method and the chlorine industry of patent CN2017111426887, the process route of the two major class UV resins of preparation of a chlorine element circulation can be formed, a new direction is specified for traditional chlor-alkali industry.

Description

Synthesis of polybasic unsaturated carboxylic ester by using 1, 3-dichloroisopropanol as initial raw material
The application is a divisional application of a method for synthesizing vinyl carboxylate, and has an original application number of 2017111426887, and an original application date of 11 months and 17 days in 2017.
Technical Field
The invention relates to polyunsaturated carboxylic ester, in particular to polyunsaturated carboxylic ester synthesized by taking 1, 3-dichloroisopropanol as a starting material and a synthesis method thereof.
Background
With the increasing attention paid to environmental protection, the coating industry is undergoing a great revolution, the market share of the traditional oil coating is less and less, and the market share of the environment-friendly coating such as water-based coating, powder coating and radiation curing (including ultraviolet light and electron beam curing, namely UV/EB curing) coating is larger and larger.
Among them, radiation curing, especially UV curing coatings, are receiving more and more attention from people because of their mild curing conditions and wide applicability. The UV curing coating can be prepared from the water-based UV resin, has higher curing speed than the traditional water-based coating, and obviously improves the film coating performance; the UV powder coating can be prepared by adopting the UV resin with high melting point, has lower construction temperature (lower than 140 ℃, even can be constructed at 80 ℃) than the traditional powder coating, can be applied to the fields of plastics, wood, paper and the like except metal, and more remarkably solves the defect of poor leveling property of the traditional powder coating because the UV powder coating is firstly sprayed and then cured.
The resin for the UV-curable coating mainly comprises: polyether acrylates, polyester acrylates, epoxy acrylates, urethane acrylates and acrylate oligomers containing specific groups, reactive monomers including condensation products of various polyols with acrylic or methacrylic acid, vinyl ether series, epoxy series, etc.
The UV curing mode comprises free radical initiation and cationic initiation, wherein the free radical initiation has the advantage of high reaction speed and has the defect of high shrinkage; the cationic initiation reaction rate is slower than radical initiation but much faster than conventional thermal curing, with the outstanding advantages of low shrinkage, excellent adhesion and thermal stability. Since the UV curable resins currently on the market are mainly acrylate derivatives, the main initiation mode is free radical initiation; cationic initiated UV resins mainly include vinyl ether series and epoxy series.
The N-vinyl caprolactam and vinyl ether series products have similar production processes, all adopt acetylene as a raw material, are mainly used for preparing high-performance materials through free radical polymerization, can also be used for monomers of photocuring coatings, have high curing conversion rate in a cation/free radical hybrid system, and have lower shrinkage and higher adhesive force compared with acrylate series products. The monomers with similar performance to the N-vinyl caprolactam also comprise N-vinyl pyrrolidone and N-vinyl imidazole, and the application of the resin monomers is greatly limited because the synthesis of the resin monomers is difficult, the technology is often monopolized by a large company, and the product price is higher.
Another major class of vinyl derivatives is vinyl carboxylates. Different from vinyl ether and N-vinyl derivatives, the nucleophilic property of carboxylate radical is too weak, so that the technological conditions for preparing vinyl carboxylate by acetylene method are more rigorous, only a few varieties of vinyl carboxylate actually realizing industrialization exist, and most representative are vinyl acetate and vinyl versatate. There are no vinyl ester monomers or resins currently on the market for use in photocurable coatings, which may be that the existing monomers are not suitable as UV coating components and do not represent vinyl carboxylates that cannot be used as resins or monomer components for UV coatings.
The most main application of the vinyl acetate comprises the preparation of PVAc and PVA, the preparation of EVA emulsion by copolymerization with ethylene, the preparation of vinyl acetate-acrylic emulsion by copolymerization with acrylic ester, the preparation of tertiary acetate emulsion by copolymerization with tertiary ethylene carbonate and the like; the vinyl versatate contains a branched group, and can provide good ultraviolet resistance, weather resistance, oil resistance, water resistance and the like when being added into emulsion as a monomer. The photocuring coating needs to meet the requirement of environmental protection, no low-boiling-point monomer is added, and a monofunctional group monomer is rarely added in order to ensure the performance of a curing film, so that the two vinyl carboxylate products are not suitable for being used as UV monomers.
A series of vinyl carboxylate esters can be prepared by adopting patent CN2017111426887, and the vinyl carboxylate esters comprise mono-component, di-component, tri-component and multi-component fatty acid vinyl esters, aromatic acid vinyl esters and multi-component vinyl esters containing carbonyl, ether bond, thioether bond, ester bond and peptide bond. Some of the monomers or resins can meet the performance requirements of the UV coating on the resin, and even some of the polycarboxylic acid vinyl esters containing special groups can improve the defects in the existing resin varieties, thereby further perfecting the application field of the UV curing coating.
Disclosure of Invention
Some of the literature-accessible physical properties of vinyl carboxylates are given in tables 1-4. These vinyl carboxylates can be prepared by the corresponding carboxylic acids according to the synergic method of patent CN 2017111426887. Vinyl acetate and C9-C11 vinyl versatate have more mature synthesis processes in industry, and the synthesis process is not required. Wherein,
table 1 is a vinyl ester of a monobasic fatty acid containing only one unsaturated bond;
table 2 shows vinyl esters of monobasic fatty acids containing two or more unsaturated bonds;
table 3 is a dibasic fatty acid vinyl ester having two or more unsaturated bonds;
table 4 shows vinyl esters of mono-or polybasic aromatic acids.
The reaction of phosgene with aldehyde or ketone under the action of catalyst can obtain carbonate of enol ester, and Table 5 shows some physical characteristics of the products of diethylene carbonate and diisopropenyl carbonate under the action of catalyst.
The data are from SCID database, wherein both experimental data and prediction data exist, and error possibly exists between the experimental data and the prediction data and the actual data, and the data are only used as reference, and the actual experimental data is taken as the standard.
In addition, some carboxylic acids containing hydroxyl groups can prepare polybasic acyl chloride intermediates containing carbonate groups by a phosgene method, and finally obtain polybasic carboxylic acid vinyl esters containing carbonate groups through a synergistic reaction. Which comprises the following steps:
obtaining 2, 2' -carbonyl dioxy-divinyl dipropionate by using lactic acid as starting raw material
，
4, 4' -carbonyl dioxy-divinyl bis benzoate is obtained by taking p-hydroxybenzoic acid as a starting raw material
，
Obtaining 12, 12' -carbonyl dioxy-divinyl dioleate from ricinoleic acid as initial raw material
，
2, 2' -carbonyl dioxy-divinyl succinate obtained by using malic acid as starting material
，
Using citric acid as initial raw material to obtain 2, 2' -carbonyldioxy-bis (propane-1, 2, 3-tricarboxylic acid) hexavinyl ester
，
The poly carbonic acid (1, 2-diethylene oxygen carbonyl glycol) ester resin is obtained by using tartaric acid as a starting material
。
Partial amino acid can be prepared into a ureido-containing polybasic acyl chloride intermediate through a phosgene method, and finally the ureido-containing polybasic carboxylic acid vinyl ester is obtained through a synergistic reaction. Which comprises the following steps:
obtaining N, N' -carbonyl diphenyl alanine divinyl ester by taking phenylalanine as initial raw material
，
Method for preparing N, N' -carbonyl-biaspartic acid tetraethenyl ester by using aspartic acid as starting raw material
，
Obtaining N, N' -carbonyl-di-methionine divinyl ester by using methionine as initial raw material
，
Obtaining N, N' -carbonyl-dithio-glutamic acid tetraethenyl ester by using glutamic acid as starting material
，
(1-ethyleneoxycarbonyl) pentamethylene diamine polyurea resin obtained by using lysine as initial raw material
。
The vinyl ester products have different physical properties, different raw material sources and different synthesis costs, so the functions and application fields of the vinyl ester products in a UV coating system are also emphasized. For example, low molecular weight monovinylic esters are not suitable as monomers for direct use in UV coatings, but can be used to prepare prepolymer resins; binary low viscosity vinyl esters can be used in reactive diluents; the vinyl ester prepared by adopting natural carboxylic acid can be used for UV coating for food packaging; polyvinylesters having melting points above 60 ℃ are useful as UV powder coating resins, and the like.
While the synergistic method of patent CN2017111426887 is adopted to obtain vinyl carboxylate products with different functions, it is not negligible that a large amount of chlorohydrins as byproducts are produced simultaneously, such as ethylene oxide, propylene oxide, and epichlorohydrin are used as absorption reagents to obtain 2-chloroethanol, 1-chloroisopropanol, and 1, 3-dichloroisopropanol, respectively. The chlorohydrin can be sold as a chemical raw material, but has low additional value and insignificant economic benefit. If the chlorohydrin can be further derivatized to obtain a product with higher added value, the comprehensive cost is greatly reduced, and obvious environmental protection benefits can be brought through process optimization.
The 1, 3-dichloroisopropanol containing two chlorine atoms has larger application space compared with other chlorohydrins.
An industrial synthesis process of epichlorohydrin uses glycerin as raw material, and the glycerin reacts with hydrochloric acid under the action of a catalyst to obtain two useful dichloro derivatives: 2, 3-dichloropropanol and 1, 3-dichloropropanol
，
The epichlorohydrin can be obtained by the reaction of two types of isopropanol and sodium hydroxide. Therefore, 1, 3-dichloroisopropanol can be used as a raw material for synthesizing epichlorohydrin, which is also the most important industrial application of 1, 3-dichloroisopropanol so far.
One skilled in the art can readily understand from the relevant technical books that another use for 1, 3-dichloroisopropanol is in the preparation of organic amines or quaternary ammonium salts. For example, 1, 3-dichloroisopropanol reacts with strong ammonia water under certain conditions to obtain 2-hydroxypropanediamine, reacts with alkyl primary amine to obtain 2-hydroxypropanebis (alkyl secondary amine), reacts with dialkyl secondary amine to obtain 2-hydroxypropanebis (dialkyl tertiary amine), and reacts with trialkyl tertiary amine to obtain 2-hydroxypropanebis (trialkyl quaternary ammonium salt).
Such as 1, 3-dichloroisopropanol with N, N-dimethylhexadecylamine to obtain a Gemini quaternary ammonium salt (formula 13)
，
The hydroxyl group in the formula (13) is further added with a dibasic acid anhydride such as maleic anhydride and then neutralized to obtain a gemini surfactant (formula 14) having both anion and cation and having a polymerizable double bond
，
The surfactant can be used as a reactive emulsifier or dispersant for aqueous emulsions.
Similarly, 1, 3-dichloroisopropanol with a carboxylate salt in the presence of a catalyst may also produce a carboxylate ester. Certain saturated dicarboxylic acid esters may be used as plasticizers, while di-or poly-unsaturated carboxylic acid esters may be used as reactive monomers or resins for free-radically initiated UV coatings, which is certainly a more valuable field of application.
Three types of unsaturated carboxylic acid esters can be prepared using 1, 3-dichloroisopropanol as a starting material.
(1) The two chlorine atoms of 1, 3-dichloroisopropanol firstly react to obtain the product with the structure (formula 15)
，
Wherein R is1、R2Each independently is H or methyl;
R3is OH or、、、、Or R is4M and M are H or Na or K;
R4is composed of、、、、、。
The synthesis method comprises the following steps: the sodium chloride is prepared by dechlorinating 1, 3-dichloroisopropanol, sodium acrylate, sodium methacrylate, sodium crotonate and 2-methyl-2-sodium crotonate under the action of a catalyst; or 1, 3-dichloroisopropanol, sodium acrylate, sodium methacrylate, sodium crotonate and 2-methyl-2-sodium crotonate are used for dechlorinating sodium under the action of a catalyst, and then continuously react with allyl chloride, epoxy chloropropane, acryloyl chloride, methacryloyl chloride and crotonyl chloride in the presence of alkali (such as sodium hydroxide, triethylamine and the like), in particular, another product 1,2, 3-trichloropropane prepared by glycerol and hydrochloric acid can be obtained by dechlorinating sodium with allyl alcohol and glycidol in the presence of alkali or with sodium acrylate, sodium methacrylate and sodium crotonate under the action of a catalyst; or 1, 3-dichloroisopropanol, sodium acrylate, sodium methacrylate, sodium crotonate and 2-methyl-2-sodium crotonate are used for dechlorinating sodium under the action of a catalyst, and then the sodium crotonate is continuously reacted with maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, itaconic anhydride and glutaric anhydride to obtain the compound, or the compound is neutralized by sodium hydroxide or potassium hydroxide. The catalyst used is a quaternary ammonium salt including, but not limited to: tetraethylammonium halide, tetrabutylammonium halide, hexadecyltrimethylammonium halide, benzyltrimethylammonium halide, where the halogen is chlorine or bromine.
(2) 1, 3-dichloroisopropanol is firstly reacted with phosgene to obtain the product with the structure of formula 16
，
Wherein R is1、R2Each independently is H or methyl.
The synthesis method comprises the following steps: 1, 3-dichloroisopropanol and phosgene are firstly synthesized into bis (1, 3-dichloroisopropyl) carbonate, and then sodium acrylate, sodium methacrylate, sodium crotonate and sodium 2-methyl-2-crotonate are dechlorinated under the action of a catalyst to obtain the product. The catalyst used is a quaternary ammonium salt including, but not limited to: tetraethylammonium halide, tetrabutylammonium halide, hexadecyltrimethylammonium halide, benzyltrimethylammonium halide, where the halogen is chlorine or bromine.
(3) The hydroxyl group of 1, 3-dichloroisopropanol is firstly reacted to obtain the product with the structure of (formula 17)
，
Wherein R is1、R2Each independently is H or methyl;
R4is composed of、、、、、；
n≥1。
The synthesis method comprises the following steps: reacting 1, 3-dichloroisopropanol with maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, itaconic anhydride, and glutaric anhydride, and neutralizing with sodium hydroxide to obtain sodium salt with structure (formula 18)
，
Then dechlorinated with sodium acrylate, sodium methacrylate, sodium crotonate and 2-methyl-2-sodium crotonate according to certain molar ratio under the action of catalyst. The catalyst used is a quaternary ammonium salt including, but not limited to: tetraethylammonium halide, tetrabutylammonium halide, hexadecyltrimethylammonium halide, benzyltrimethylammonium halide, where the halogen is chlorine or bromine. The molar ratio of the sodium salt with the structure of (formula 18) to sodium acrylate, sodium methacrylate, sodium crotonate and 2-methyl-2-sodium crotonate is 1: 1-1: 2.
In the unsaturated carboxylic ester synthesized by taking 1, 3-dichloroisopropanol as the starting material, the unsaturated carboxylic ester not only has micromolecular liquid resin with binary structure, but also has hydrophilic resin containing carboxylate groups, and also comprises hyperbranched powdery resin which is connected by carbonic ester and can be used for UV powder coating, and linear multi-side chain vermicular polyester type unsaturated resin. Most of these unsaturated carboxylic acid esters are useful in UV curable coatings, which is a beneficial complement to the existing acrylate UV resins on the market, but the significance of the present invention is far from being so.
The invention has more valuable significance in that a technological route for preparing two types of UV resin by circulating chlorine elements can be formed by combining the invention with the industries of preparing vinyl carboxylate by a synergistic method, preparing epoxy chloropropane by a glycerin method and preparing chlor-alkali by a patent CN 2017111426887. See (figure 1).
A general reaction route is given in (figure 1), and the specific reaction relates to various factors such as a catalyst, other materials, processes and the like; the chlorine element circulation does not represent that no foreign chlorine element enters, such as sodium chloride, hydrochloric acid, epichlorohydrin and the like which are used as bulk chemicals are needed to determine whether outsourcing (or selling) is needed according to cost accounting; also, some products are not shown in the figure 1, such as hydrogen produced by electrolysis of saturated sodium chloride solution, carbon dioxide produced by preparation of acyl chloride by phosgene, and the like; the dichloropropanol prepared by the glycerol method is slightly different from the dichloropropanol by-product in the preparation of vinyl carboxylate, wherein the dichloropropanol is a mixture of 2, 3-dichloropropanol and 1, 3-dichloropropanol, and the dichloropropanol by-product in the preparation of vinyl carboxylate is a substance of 1, 3-dichloropropanol, but both can be used for preparing epichlorohydrin and can also be used for preparing unsaturated carboxylic ester.
Through the circulation, the emission to the environment is greatly reduced, the comprehensive cost is reduced to the maximum extent, and the final UV resin product is more competitive in the market; most importantly, the process route has remarkable economic benefit and social benefit, and indicates a new direction for the traditional chlor-alkali industry.
Drawings
Fig. 1 is a schematic process route for preparing two types of UV resins in a chlorine element cycle, which is formed by combining the synergistic method for preparing vinyl carboxylate, the glycerol method for preparing epichlorohydrin and the chlor-alkali industry of patent CN 2017111426887. In the process route, initial chlorine elements are from (1) sodium chloride, (1) sodium chloride is electrolyzed to prepare (2) chlorine by-product sodium hydroxide, (2) chlorine is combined with carbon monoxide to prepare (3) phosgene, (3) phosgene is reacted with carboxylic acid to obtain (4) acyl chloride and by-product (5) hydrochloric acid, (5) hydrochloric acid is reacted with glycerin to obtain (6) dichloroisopropyl alcohol, (6) dichloroisopropyl alcohol is reacted with sodium hydroxide to obtain (7) epichlorohydrin and by-product (1) sodium chloride, (4) acyl chloride is reacted with acetaldehyde to obtain (8) 1-chloroethyl carboxylic ester, (8) 1-chloroethyl carboxylic ester is reacted with (7) epichlorohydrin to obtain vinyl carboxylate and by-product (6) dichloroisopropyl alcohol, unsaturated carboxylic acid is reacted with sodium hydroxide to obtain unsaturated sodium carboxylate, then reacting with (6) dichloroisopropanol to obtain unsaturated carboxylic ester and by-product (1) sodium chloride.
Detailed Description
Table 6 shows the physical properties of the partially polyunsaturated carboxylic acid esters represented by (formula 15) which can be produced by the present invention.
The intermediate of the product represented by (formula 16) is represented by (formula 19)
，
The quaternary unsaturated carbonate resin listed in (formula 20) can be prepared by (formula 19), and this multi-branched resin has crystallinity, has low viscosity after melting, and can be used for UV powder coating.
Unlike the small molecular weight polybasic unsaturated carboxylic acid ester shown in the structures (15) and (16) which can prepare high-content single substance, the polybasic unsaturated carboxylic acid ester shown in the structure (17) is a linear multi-side chain worm-shaped polyester type unsaturated resin obtained by polycondensation, and the molecular weight of the resin is different from hundreds to thousands according to the different molar ratios of the sodium salt of the structure (18) to sodium acrylate, sodium methacrylate, sodium crotonate and 2-methyl-2-sodium crotonate. The linear multi-side chain vermicular polyester unsaturated resin not only contains hydrophilic groups, but also has good compatibility with water and can be used as resin for water-based UV coating; the side chains can ensure that the viscosity of the solid resin is moderate after the solid resin and other resins are compounded, heated and melted, and the resin can be used as a resin for UV powder coating.
The following examples take maleic anhydride and sodium acrylate as raw materials, and the specific synthesis method is as follows: putting 98g of maleic anhydride into a 1000mL three-neck flask, dissolving with 300g of tetrahydrofuran, refluxing (60-66 ℃), dripping 129g (1 mol) of 1, 3-dichloroisopropanol, and continuing to carry out reflux reaction for 1-2 h after finishing dripping for 2 h; cooling to normal temperature, centrifuging to filter out most of crystals, recovering tetrahydrofuran under reduced pressure to obtain the rest crystals, and mixing the crystals; dissolving the crystal with 30% liquid alkali, adjusting the pH of the solution to 8-9, concentrating, crystallizing and drying to obtain about 240g of sodium salt (maleic acid ester monosodium salt, hereinafter referred to as monosodium salt) of formula 18. The amount of substance was calculated from the molecular weight of the monosodium salt, and the mixture was mixed in a molar ratio different from that of sodium acrylate, and the mixture was refluxed (about 150 ℃ C.) for 4 to 8 hours in the presence of N, N-dimethylformamide as a solvent and tetrabutylammonium chloride as a catalyst, and the thus purified polyunsaturated carboxylic acid ester was as shown in Table 7.

Claims (5)

1. The method for synthesizing the polybasic unsaturated carboxylic ester by using 1, 3-dichloroisopropanol as a starting material is characterized in that the polybasic unsaturated carboxylic ester has a structure represented by (formula 17):
wherein,
R1、R2each independently is H or methyl;
R4is composed of、、、、、；
n≥1。
2. A method for synthesizing the polybasic unsaturated carboxylic acid ester according to claim 1, wherein the polybasic unsaturated carboxylic acid ester represented by the structure (formula 17) is obtained by reacting 1, 3-dichloroisopropanol with maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, itaconic anhydride, glutaric anhydride and neutralizing with sodium hydroxide
，
Then dechlorinated with sodium acrylate, sodium methacrylate, sodium crotonate and 2-methyl-2-sodium crotonate according to certain molar ratio under the action of catalyst.
3. The process according to claim 2, wherein the catalyst used is a quaternary ammonium salt.
4. The process according to claim 2, wherein the catalyst used comprises: tetraethylammonium halide, tetrabutylammonium halide, hexadecyltrimethylammonium halide, benzyltrimethylammonium halide, where the halogen is chlorine or bromine.
5. The method for synthesizing the polyunsaturated carboxylic acid ester according to claim 2, wherein the molar ratio of the sodium salt of the structure (formula 18) to the sodium acrylate, the sodium methacrylate, the sodium crotonate and the sodium 2-methyl-2-crotonate is 1: 1 to 1: 2.
CN201711440992.XA 2017-11-17 2017-11-17 Multi-unsaturated carboxylic acid's ester is synthesized by starting material of 1,3- dichloroisopropanols Pending CN108003028A (en)

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CN110327842B (en) * 2019-07-15 2021-07-13 四川轻化工大学 Octafluoropentanol-based fluorine-containing surfactant and preparation method thereof
CN113683942A (en) * 2021-09-27 2021-11-23 成都普利美特科技有限公司 Polyimide water-based epoxy coating and preparation method thereof

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Application publication date: 20180508