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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unsaturated carboxylic
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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

Multi-unsaturated carboxylic acid's ester is synthesized by starting material of 1,3- dichloroisopropanols
The application is《A kind of method of synthesis of carboxylic acid vinyl acetate》Divisional application, original applying number 2017111426887, Original application day is on November 17th, 2017.
Technical field
The present invention relates to multi-unsaturated carboxylic acid's ester, and in particular to 1,3- dichloroisopropanols for starting material synthesis it is more First esters of unsaturated carboxylic acids and its synthetic method.
Background technology
As people increasingly pay attention to environmental protection, huge change, traditional oil are also occurring for coating industry Property Coating Market share is fewer and fewer, coating such as water paint, powdery paints, the radiation curing of environment-friendly type（Including ultraviolet light with Electronic beam curing, that is, UV/EB cures）Coating Market share is then increasing.
Wherein radiation curing particularly UV is coating material solidified because its condition of cure is gentle, applicability is wide, is increasingly subject to people Attention.UV is coating material solidified can to prepare aqueous UV curing coating using water-based UV resins, cure speed than traditional water paint Faster, film performance is also significantly increased degree；UV powdery paints can be prepared using dystectic UV resins, compare traditional powder coating Construction temperature is lower（Less than 140 DEG C, it might even be possible in 80 DEG C of constructions）, can be applied to plastics beyond metal, timber, paper etc. Field, more prominent is due to that UV powdery paints is first to spray solidify afterwards, solves levelling difference existing for traditional powder coating Defect.
UV is coating material solidified mainly to be included with resin：Polyether acrylate, polyester acrylate, epoxy acrylate, poly- ammonia Ester acrylate and the acrylate oligomer containing specific groups, activated monomer include various polyalcohols and acrylic acid or first The condensation product of base acrylic acid, vinyl ethers series, epoxy series etc..
UV curing modes include that free radical triggers and cation triggers, and wherein free radical triggers with fast excellent of reaction speed Point, shortcoming are shrinking percentage height；Cation rate of initiation reaction relative free-radical trigger it is slow some but it is faster than conventional heat cure More, outstanding advantages are that low shrinking percentage, adhesive force and heat endurance are outstanding.Since UV solidified resins currently on the market are mainly third Olefin(e) acid ester derivative, therefore main initiation method is that free radical triggers；Cation triggers UV resins mainly to include vinyl Ether series and epoxy series.
N- caprolactams and vinethene series of products have similar production technology, all using acetylene as former Material, is mainly used for radical polymerization and prepares high performance material, it can also be used to the monomer of photocureable coating, in cation/freedom Cure high conversion rate in base hybrid systems, with respect to series of acrylate, shrinking percentage is lower, adhesive force higher.With N- vinyl oneself The monomer that lactams has similar performance further includes n-vinyl pyrrolidone, N- vinyl imidazoles, these resin monomers due to Synthesis is difficult, and technology is often monopolized by major company, and product price is higher, strongly limit its application.
Another major class ethenyl derivatives are vinyl carboxylates.Unlike vinethene and N- ethenyl derivatives, by Too weak in the nucleophilicity of carboxylate radical, it is harsher to prepare the process conditions of vinyl carboxylates with acetylene method, really realizes industrialization Vinyl carboxylates only have a small number of several kinds, most representational is vinylacetate and tertiary ethylene carbonate.City at present There is no vinyl esters monomer or resin to be applied to photocureable coating on face, this is probably that existing monomer is not appropriate for applying as UV Expect component, do not represent resin or monomer component that vinyl carboxylates cannot function as UV coating.
The main purposes of vinylacetate includes preparing PVAc, PVA, EVA lotions is prepared with ethylene copolymer, with acrylic acid Ester copolymerization prepares acrylate and vinyl acetate emulsion, and tertiary vinegar milk liquid etc. is prepared with tertiary ethylene carbonate copolymerization；Tertiary ethylene carbonate contains branched group, Good uvioresistant, weatherability, oil resistivity and water resistance etc. can be provided in lotion as monomer addition.Since photocuring applies Need to meet environmental requirement in material, low boiling point monomer will not be added, in order to ensure that the performance of cured film also seldom adds simple function Single group body, therefore, above two vinyl carboxylates product are not suitable as UV monomers.
A series of vinyl carboxylates, including unitary, binary, ternary can be prepared using patent CN2017111426887 And polynary fatty acid vinyl ester, fragrant vinyl acetate and containing carbonyl, ehter bond, thioether bond, ester bond, peptide bond polynary ethene Ester.Always there are some to meet performance requirement of the UV coating for resin in these monomers or resin, in addition it is some containing special The polybasic carboxylic acid vinyl acetate of group can improve defect present in existing resin variety, further improve UV it is coating material solidified should Use field.
The content of the invention
Table 1-4 gives the part physical property characteristic for the vinyl carboxylates that part document can be looked into.These vinyl carboxylates pass through Corresponding carboxylic acid can be prepared according to the collaboration method of patent CN2017111426887.Vinyl acetate and C9 ~ C11 versatic acid second Enester is synthesized due to industrially there is more ripe synthesis technique without this technique.Wherein,
Table 1 is the unary fatty acid vinyl acetate only containing a unsaturated bond；
Table 2 is the unary fatty acid vinyl acetate containing two or more unsaturated bond；
Table 3 is the di-fatty vinyl acetate containing two or more unsaturated bond；
Table 4 is unitary or polynary fragrant vinyl acetate.
Carbonic acid enol ester can be obtained by directly being reacted with phosgene and aldehydes or ketones under catalyst action, and table 5 is acetaldehyde and third The part physical property characteristic of ketone and product divinyl carbonate and carbonic acid diisopropyl enester of the phosgene under catalyst action.
Data above is all from SCIfinder databases, wherein existing experimental data also has prediction data, may with it is true Data there are error, For Information Only is subject to the experimental data of reality.
In addition, some carboxylic acids for containing hydroxyl can be made by phosgenation among the polynary acyl chlorides containing carbonate group Body, the polybasic carboxylic acid vinyl acetate containing carbonate group is finally obtained by concerted reaction.Including：
2,2 '-carbonyl dioxygen-bis- propionic acid diethyl enester is obtained by starting material of lactic acid
,
4,4 '-carbonyl dioxygen-bis- benzoic acid diethyl enester is obtained by starting material of P-hydroxybenzoic acid
,
12,12 '-carbonyl dioxygen-bis- oleic acid diethyl enester is obtained by starting material of ricinoleic acid
,
2,2 '-carbonyl dioxygen-four vinyl acetate of bis- butanedioic acids is obtained by starting material of malic acid
,
2,2 '-carbonyl dioxygen-bis- (propane -1,2,3- tricarboxylic acids) six vinyl acetates are obtained by starting material of citric acid
,
Poly- carbonic acid is obtained by starting material of tartaric acid（1,2- divinyl oxide carbonyl ethylene glycol）Ester resin
。
The polynary acid chloride intermediate containing urea groups can be made by phosgenation in partial amino-acid, final by concerted reaction Obtain the polybasic carboxylic acid vinyl acetate containing urea groups.Including：
N is obtained by starting material of phenylalanine, N '-carbonyl connects two phenylalanine divinyl esters
,
N is obtained by starting material of asparatate, N '-carbonyl connects two asparatates, four vinyl acetate
,
N is obtained by starting material of methionine, N '-carbonyl connects two methionine diethyl enesters
,
N is obtained by starting material of glutamic acid, N '-carbonyl connects two glutamic acid, four vinyl acetate
,
(1- vinyloxycarbonyls) pentanediamine carbamide resin is obtained by starting material of lysine
。
Physical difference, raw material sources difference, synthesis cost in above-mentioned vinyl acetate product due to itself is different, it is applied in UV Effect and application field in material system also emphasize particularly on different fields.Unitary vinyl acetate such as low molecular weight is not suitable for directly using as monomer In UV coating, but can be used for preparing prepolymer resin；The low viscosity vinyl acetate of binary can be used for reactive diluent；Using natural Vinyl acetate prepared by carboxylic acid can be used for food packaging UV coating；Polynary vinyl acetate of the fusing point higher than 60 DEG C can be used as UV powder to apply Expect resin, etc..
While the vinyl carboxylates product of Various Functions is obtained using the collaboration method of patent CN2017111426887, It is very important, while generate substantial amounts of accessory substance chlorhydrin, such as using ethylene oxide, propylene oxide, epoxychloropropane as Absorption reagent respectively obtains ethylene chlorhydrin, 1- chloro isopropanols, 1,3- dichloroisopropanols.Although chlorhydrin can be used as industrial chemicals Sell, but its added value is low, and economic benefit is not notable.If the further derivatization of chlorhydrin can be obtained more high added value Product, comprehensive cost will be greatly reduced, by process optimization, and significant environmental benefit may be brought.
The relatively other chlorhydrins of 1,3- dichloroisopropanols wherein containing two chlorine atoms have the application space of bigger.
A kind of industrial synthesis technique of epoxychloropropane is exactly using glycerine as raw material, and glycerine is with hydrochloric acid in catalyst action Lower reaction, can obtain two kinds of useful dichloro-derivatives：2,3- dichlorohydrins and 1,3- dichloroisopropanols
,
Two kinds of isopropanols can obtain epoxychloropropane with sodium hydroxide reaction.Therefore, 1,3- dichloroisopropanols can conduct The raw material of synthesizing epoxy chloropropane, this is also most important industrial applications of 1,3- dichloroisopropanols so far.
Those skilled in the art can will readily recognize that 1,3- dichloroisopropanols are another by relevant professional book Kind purposes is to prepare organic amine or quaternary ammonium salt.It can be obtained as 1,3- dichloroisopropanols react under certain conditions with concentrated ammonia liquor 2- hydroxyl propane diamine, 2- hydroxyls the third two can be obtained with kiber alkyl amine reaction（Alkyl secondary amine）, can be with dialkylamine reaction Obtain 2- hydroxyls the third two（Dialkyl group tertiary amine）, 2- hydroxyls the third two are obtained with trialkyl reactive tertiary amine（Tri alkyl quaternary ammonium salt）.
As 1,3- dichloroisopropanols and the reaction of N, N- dimethyl hexadecyl amine can obtain a kind of double type quaternary ammonium salt（Formula 13）
,
（Formula 13）In hydroxyl continue neutralized again with dibasic acid anhydride such as maleic anhydride addition, can obtain one kind have concurrently anion with Cation and the gemini surfactant containing polymerizable double bond（Formula 14）
,
The surfactant can be used for the reactive emulsifier or dispersant of water-based emulsion.
Similarly, 1,3- dichloroisopropanols can also prepare carboxylate in the presence of a catalyst with carboxylate.Some saturations Dicarboxylic esters may be used as plasticizer, and binary or polynary esters of unsaturated carboxylic acids may be used as free radical and trigger UV to apply The activated monomer or resin of material, this is undoubtedly more valuable application field.
With 1,3- dichloroisopropanols for starting material, the esters of unsaturated carboxylic acids of three types can be prepared.
（1）Two chlorine atoms of 1,3- dichloroisopropanol are reacted first, can obtain（Formula 15）The product of structure
,
Wherein, R1、R2Each stand alone as H or methyl；
R3For OH or、、、、, or R4M, M are H or Na or K；
R4For、、、、、。
Synthetic method is：With 1,3- dichloroisopropanols and sodium acrylate, Sodium methacrylate, butenoic acid sodium, 2- methyl -2- Butenoic acid sodium under catalyst action dechlorination sodium and obtain；Or with 1,3- dichloroisopropanols and sodium acrylate, methacrylic acid Sodium, butenoic acid sodium, 2- methyl-2-butenoic acids sodium the dechlorination sodium under catalyst action, then proceed to and allyl chloride, epoxy chlorine Propane, acryloyl chloride, methacrylic chloride, crotonyl chloride are in alkali（Such as sodium hydroxide, triethylamine）In the presence of react and obtain, it is special Not, 1,2,3- trichloropropane of another product made from glycerine and hydrochloric acid can with allyl alcohol, glycidol in the presence of a base or Dechlorination sodium obtains under catalyst action with sodium acrylate, Sodium methacrylate, butenoic acid sodium；Or with 1,3- dichloro isopropyls Alcohol and sodium acrylate, Sodium methacrylate, butenoic acid sodium, 2- methyl-2-butenoic acids sodium the dechlorination sodium under catalyst action, so Continue to react with maleic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, succinic anhydride, itaconic anhydride, glutaric anhydride afterwards And obtain, or neutralized and obtained with sodium hydroxide or potassium hydroxide.Catalyst used is quaternary ammonium salt, is included but not limited to：Tetrem Base ammonium halide, tetrabutyl ammonium halide, cetyl trimethyl ammonium halide, benzyl trimethyl ammonium halide, wherein halogen are chlorine or bromine.
（2）1,3- dichloroisopropanol with phosgene reaction, can obtain first（Formula 16）The product of structure
,
Wherein, R1、R2Each stand alone as H or methyl.
Synthetic method is：Two (1,3- bis- chloro isopropyl) carbonic esters are synthesized with 1,3- dichloroisopropanols and phosgene first, so Afterwards with sodium acrylate, Sodium methacrylate, butenoic acid sodium, 2- methyl-2-butenoic acids sodium under catalyst action dechlorination sodium and .Catalyst used is quaternary ammonium salt, is included but not limited to：Tetraethyl ammonium halide, tetrabutyl ammonium halide, cetyl trimethyl Ammonium halide, benzyl trimethyl ammonium halide, wherein halogen are chlorine or bromine.
（3）The hydroxyl of 1,3- dichloroisopropanols reacts first to be obtained（Formula 17）The product of structure
,
Wherein, R1、R2Each stand alone as H or methyl；
R4For、、、、、；
n≥1。
Synthetic method is：With 1,3- dichloroisopropanols and maleic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, Succinic anhydride, itaconic anhydride, glutaric anhydride react and neutralize to obtain with sodium hydroxide（Formula 18）The sodium salt of structure
,
Then exist with sodium acrylate, Sodium methacrylate, butenoic acid sodium, 2- methyl-2-butenoic acids sodium according to certain molar ratio Dechlorination sodium under catalyst action and obtain.Catalyst used is quaternary ammonium salt, is included but not limited to：Tetraethyl ammonium halide, four fourths Base ammonium halide, cetyl trimethyl ammonium halide, benzyl trimethyl ammonium halide, wherein halogen are chlorine or bromine.（Formula 18）Structure The molar ratio of sodium salt and sodium acrylate, Sodium methacrylate, butenoic acid sodium, 2- methyl-2-butenoic acid sodium is 1: 1~1: 2.
In esters of unsaturated carboxylic acids with 1,3- dichloroisopropanols for starting material synthesis, the small molecule liquid of existing diadactic structure Body resin, also there is the hydrophilic resin of carboxylate-containing group, further includes the over-expense available for UV powdery paints of carbonic ester connection Change powdery resin, and linear more side chain vermiform polyester-type unsaturated-resins.Most of these esters of unsaturated carboxylic acids are available It is coating material solidified in UV, it is the useful supplement to the existing esters of acrylic acid UV resins of in the market, and meaning of the present invention is far above So.
The more valuable meaning of the present invention is, the present invention and patent CN2017111426887 are cooperateed with legal system carboxylic acid Vinyl acetate, preparing epoxy chloropropane by using glycerol method and chlorine industry are combined, and the preparation two that can form a chlorine element circulation is big The process route of class UV resins.Referring to（Attached drawing 1）.
（Attached drawing 1）In give a general reaction scheme, specific reaction is related to catalyst, other materials, technique Deng many factors；Chlorine element circulation does not represent no external chlorine element yet and enters, such as sodium chloride, hydrochloric acid, epoxychloropropane Deng as bulk chemical being to need according to cost accounting to determine the need for outsourcing（Or sell）'s；Equally there are some products It is not marked on（Attached drawing 1）In, such as sodium chloride saturated solution electrolysis meeting by-product hydrogen, phosgene acyl chlorides has carbon dioxide generation Deng；Dichloroisopropanol prepared by glycerine method is slightly different with preparing the dichloroisopropanol of vinyl carboxylates by-product, the former is 2,3- The mixture of dichlorohydrin and 1,3- dichloroisopropanol, the latter 1, a kind of material of 3- dichloroisopropanols, but the two can make Standby epoxychloropropane, also may be used to prepare esters of unsaturated carboxylic acids.
By above-mentioned circulation, the discharge to environment is greatly reduced, farthest reduces comprehensive cost, is also caused Final UV naval stores is more competitive in the market to be possibly realized；The most key, which has significant warp Benefit of helping and social benefit, a new direction is specified for traditional chlor-alkali industry.
Brief description of the drawings
Attached drawing 1 is to cooperate with the legal system vinyl carboxylates, glycerine method to prepare ring with patent CN2017111426887 the present invention The process route that oxygen chloropropane and chlorine industry are combined the two major class UV resins of preparation of the chlorine element to be formed circulation shows It is intended to.In the process route, the chlorine element of starting comes from（1）Sodium chloride,（1）Sodium chloride is through electrolytic preparation（2）Chlorine by-product Sodium hydroxide,（2）Chlorine is prepared with carbon monoxide chemical combination（3）Phosgene,（3）Phosgene is obtained with carboxylic acid reaction（4）Acyl chlorides and by-product （5）Hydrochloric acid,（5）Hydrochloric acid is obtained with glycerine reaction（6）Dichloroisopropanol,（6）Dichloroisopropanol reacts to obtain with sodium hydroxide（7） Epoxychloropropane and by-product（1）Sodium chloride,（4）Acyl chlorides reacts to obtain with acetaldehyde（8）1- chloroethyl carboxylates,（8）1- chloroethyls Carboxylate with（7）Epichlorohydrin reaction obtains vinyl carboxylates and by-product（6）Dichloroisopropanol, unsaturated carboxylic acid and hydroxide Sodium reacts to obtain unsaturated carboxylic acid sodium, Ran Houyu（6）Dichloroisopropanol reacts to obtain esters of unsaturated carboxylic acids and by-product（1）Chlorination Sodium.
Embodiment
Table 6 lists what the present invention can be prepared（Formula 15）The physical property characteristic of part multi-unsaturated carboxylic acid's ester of expression.
（Formula 16）The intermediate of the product of expression is such as（Formula 19）It is shown
,
Pass through（Formula 19）It can prepare（Formula 20）The quaternary unsaturated carbon acid ester resin listed, this highly branched chain resin have crystallization Property, viscosity is low after melting, available for UV powdery paints.
With（Formula 15）、（Formula 16）The single substance of high-content can be made in small molecule multi-unsaturated carboxylic acid ester shown in structure Difference,（Formula 17）Multi-unsaturated carboxylic acid's ester of representation is a kind of linear more side chain vermiforms obtained by polycondensation reaction Polyester-type unsaturated-resin, according to（Formula 18）Sodium salt and sodium acrylate, Sodium methacrylate, butenoic acid sodium, 2- methyl -2- fourths The molar ratio of olefin(e) acid sodium is different, and the molecular weight of resin differs from a few hundred to several thousand.This linear more side chain vermiform polyester-types are not Saturated resin both contains hydrophilic radical, and the compatibility of small-molecular-weight resin and water is good, can be used as waterborne UV coating resin；It is more Side chain can ensure hard resin and modest viscosity after the compounding heating fusing of other resins, can be used as UV powder coating resins.
Using maleic anhydride and sodium acrylate as raw material, specific synthetic method is the following example：98g cis-butenedioic anhydrides are put into In 1000mL three-necked flasks, dissolved with 300g tetrahydrofurans, reflux（60~66℃）, 1,3- dichloroisopropanols 129g is added dropwise （1mol）, it is added dropwise in 2h, continues 1 ~ 2h of back flow reaction；Room temperature is down to, most of crystal is centrifugally filtered out, is recovered under reduced pressure four Hydrogen furans, obtains remainder crystal, merges crystal；Crystal is dissolved with 30% liquid caustic soda, adjusts pH value of solution 8 ~ 9, condensing crystallizing is done It is dry to obtain（Formula 18）Sodium salt（Maleic acid esters mono-sodium salt, hereinafter referred to as mono-sodium salt）About 240g.According to the molecular weight of mono-sodium salt The amount of material is calculated, is mixed according to the molar ratio different from sodium acrylate, using n,N-Dimethylformamide as solvent, four Butyl ammonium chloride is catalyst, reflux（About 150 DEG C）4 ~ 8h is reacted, the multi-unsaturated carboxylic acid's ester being refining to obtain is as shown in table 7.

Claims (5)

1. multi-unsaturated carboxylic acid's ester is synthesized for starting material with 1,3- dichloroisopropanols, it is characterised in that multi-unsaturated carboxylic acid Ester is（Formula 17）The structure of expression：
Wherein,
R1、R2Each stand alone as H or methyl；
R4For、、、、、；
n≥1。
A kind of 2. method for synthesizing multi-unsaturated carboxylic acid's ester described in claim 1, it is characterised in that（Formula 17）Representation Multi-unsaturated carboxylic acid's ester with 1,3- dichloroisopropanols and maleic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, fourth Dicarboxylic anhydride, itaconic anhydride, glutaric anhydride react and neutralize to obtain with sodium hydroxide（Formula 18）The sodium salt of structure
,
Then exist with sodium acrylate, Sodium methacrylate, butenoic acid sodium, 2- methyl-2-butenoic acids sodium according to certain molar ratio Dechlorination sodium under catalyst action and obtain.
3. the method for synthesis multi-unsaturated carboxylic acid's ester according to claim 2, it is characterised in that catalyst used is Quaternary ammonium salt.
4. the method for synthesis multi-unsaturated carboxylic acid's ester according to claim 2, it is characterised in that catalyst bag used Include：Tetraethyl ammonium halide, tetrabutyl ammonium halide, cetyl trimethyl ammonium halide, benzyl trimethyl ammonium halide, wherein halogen are Chlorine or bromine.
5. the method for synthesis multi-unsaturated carboxylic acid's ester according to claim 2, it is characterised in that（Formula 18）The sodium of structure The molar ratio of salt and sodium acrylate, Sodium methacrylate, butenoic acid sodium, 2- methyl-2-butenoic acid sodium is 1: 1~1: 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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CN107879935A (en) 2018-04-06

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Application publication date: 20180508