CN106866740B - A kind of carboxylate and preparation method thereof - Google Patents

A kind of carboxylate and preparation method thereof Download PDF

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CN106866740B
CN106866740B CN201710030682.4A CN201710030682A CN106866740B CN 106866740 B CN106866740 B CN 106866740B CN 201710030682 A CN201710030682 A CN 201710030682A CN 106866740 B CN106866740 B CN 106866740B
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carboxylate
functional element
reaction
acid
molar ratio
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CN106866740A (en
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孙宾
朱美芳
计虎泉
江晓泽
相恒学
滕伟
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Haitai Textile (Suzhou) Co Ltd
Donghua University
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Haitai Textile (Suzhou) Co Ltd
Donghua University
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    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
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    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5373—Esters of phosphonic acids containing heterocyclic rings not representing cyclic esters of phosphonic acids

Abstract

The present invention relates to a kind of carboxylates and preparation method thereof, the DAPER for being made that end group is carboxyl is reacted by the fusion esterification between binary acid and pentaerythrite first, then the DADA that end group hydroxyl is made is reacted by the difunctional organic acid containing functional element and the melt condensation between dihydric alcohol, difunctional is selected from phosphate, carboxylic acid group and sulfydryl in difunctional organic acid containing functional element, functional element is one of P, S and N, or the combination for S and N, finally DAPER is added in DADA, final product is made by esterification between the two.The disadvantages of simply leading to single purposes, preparation process pollution environment the present invention overcomes the storage of traditional liquid type carboxylate and using difficult, structure, final carboxylate obtained is the solid of high molecular weight, the end group of molecule is reaction active groups, functional element of the inside containing 8.14~18.32wt% has many advantages, such as that thermal stability is high, widely used.

Description

A kind of carboxylate and preparation method thereof
Technical field
The invention belongs to flame retardant area, it is related to a kind of carboxylate and preparation method thereof, in particular to a kind of solid-state esterification Object and its melt condensation preparation method based on reactant polyfunctional group reactivity difference.
Background technique
With the development of China's synthetic material industry and the continuous expansion of application field, have been widely used chemical building material, The every field such as electronic apparatus, communications and transportation, space flight and aviation, household furniture, interior decoration, clothing, food, lodging and transportion -- basic necessities of life.But they are mostly Combustible material easily leads to fire, causes very big threat to safety of life and property.Therefore, the fire-retardant of polymer material becomes one A urgent problem to be solved.The mode of addition fire retardant is widely used to improve the flame retardant property of material in current each quasi polymer. The advantages that phosphorus flame retardant is efficient with it, less toxic, environmentally friendly, obtains the extensive research of domestic and international experts and scholars.
One kind (miscellaneous -10- of 9,10- dihydro-9-oxy containing DOPO that Chinese patent application publication number CN 101880395A is proposed Phospho hetero phenanthrene -10- oxide) polymer type phosphor-containing fire retardant and preparation method thereof, using the modified aromatic radical dihydric phenol of DOPO Or aromatic radical dihydric alcohol and dichloride replace phosphate to be that reactant obtains polymer type phosphor-containing fire retardant, but the fire retardant is phosphorous Measure relatively low, and additive amount reaches 15% and can be only achieved preferable flame retardant property in use process.CN1563152A is changed using DOPO Property hydroquinone or be that response matrix contains to obtain polymer-type to dichloro (bromine) the oxygen phosphorus that naphthalenediol, phenyl or naphthyl replace Phosphorus fire retardant, but precipitating reagent dosage is larger in the separation process of the fire retardant, and environmental pollution is larger.CN102304230A is used Bis- (4- hydroxyphenyl) fluorenes of 9,9- and diphenylphosphoryl dichloro or phenoxy group phosphinylidyne dichloro are that response matrix prepares the phosphorous resistance with fluorenyl Agent is fired, but its reaction process is complex, solvent needed for not easy to control and experiment need to be removed water strictly.
In conclusion fire retardant on the market is as made from the method for polymerisation in solution mostly at present, preparation process is deposited In complex process, organic solvent usage amount is big, difficult solvent recovery and the problems such as pollution environment, causes production and processing cost mistake It is high；The content of functional element (P, N, S etc.) is lower in flame retardant molecule, causes the flame retarding efficiency of fire retardant lower, needs larger Fire retardant additive amount can be only achieved ideal flame retardant effect, the additive amount of fire retardant is larger and cost is easy to cause to improve, right The other performance of material has a adverse impact；Fire retardant is mostly small-molecular-weight liquefied compound, the molecule of one side fire retardant It is poor to measure the lower compatibility made between fire retardant and high molecular polymer, fire retardant is easy to reunite in a polymer matrix, Dispersion is uneven, and there is also migration problems in use, cause the durability of fire-retardant product poor；Another aspect liquid-type Fire retardant transport, storage and in terms of all have difficulties.
Therefore, that functional element content is made using solvent-free method is higher and the relatively large solid type of molecular weight is fire-retardant Agent has very important significance.
Summary of the invention
The purpose of the present invention is overcoming traditional liquid type carboxylate to store and using difficult, preparation process pollution environment, function Can constituent content is lower, the disadvantages of molecular weight is lower, prepare a kind of preparation process less pollution, functional element content it is higher and point Son measures higher solid type carboxylate.
In order to achieve the above objectives, the technical solution adopted by the present invention are as follows:
A kind of preparation method of carboxylate, the preparation method of the carboxylate are based on reactant polyfunctional group reactivity The melt condensation method of difference, the reactivity difference refer to that the polyfunctional group in reactant is had by the influence of steric hindrance According to the sequence of reactivity from high to low condensation reaction occurs for different reactivities, polyfunctional group, and steps are as follows:
1) side group binary acid containing functional element is mixed with pentaerythrite with the molar ratio of 4:1, in inert gas shielding and Fusion esterification reaction is carried out under conditions of mechanical stirring, collects product, it is post-treated to obtain the DAPER that end group is carboxyl；It is described Functional element is phosphorus or nitrogen, two acidic-groups of side group binary acid containing functional element in side group binary acid containing functional element Reactivity it is different, the structural formula of side group binary acid containing functional element is one of following:
2) by containing functional element difunctional organic acid and dihydric alcohol mixed with the molar ratio of 1:1 or 1:2, catalysis is added Agent carries out melt condensation reaction under conditions of inert gas shielding and mechanical stirring, obtains the DADA of end group hydroxyl；It is described Reactivity bifunctional is different in difunctional organic acid containing functional element, and the difunctional is phosphate and carboxylic acid Base, carboxylic acid group and sulfydryl, two carboxylic acid groups or two phosphates, the functional element are one of P, S and N, or for S and The combination of N；
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, is collected Product, it is post-treated to obtain carboxylate.
As a preferred technical scheme:
A kind of preparation method of carboxylate as described above, in step 1), the inert gas is nitrogen or argon gas, described Churned mechanically mixing speed is 300~500rpm；The temperature of fusion esterification reaction is 180~200 DEG C, and the reaction time is 1~4h；The post-processing includes dissolution, filtering and drying.
A kind of preparation method of carboxylate as described above, the difunctional organic acid containing functional element are Phenylphosphine Acid, methylphosphonic acid, 2- carboxyethyl phenyl phosphinic acid, [(the own ring -6- base of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha) first Base] succinic acid or following one of the compound of structural formula:
The dihydric alcohol is ethylene glycol, propylene glycol or 1,4- butanediol.
A kind of preparation method of carboxylate as described above, in step 2), the catalyst is 4- toluenesulfonic acid, described The molar ratio of difunctional organic acid and catalyst containing functional element be 1:0.01, the inert gas be nitrogen or argon gas, The churned mechanically mixing speed is 300~500rpm, and the temperature of melt condensation reaction is 180~200 DEG C, when reaction Between be 1~3h.
A kind of preparation method of carboxylate as described above, which is characterized in that in step 3), the inert gas is nitrogen Or argon gas, the churned mechanically mixing speed are 300~500rpm, the time of the fusion esterification reaction is 1~4h, described Post-processing includes crushing, dissolving, being filtered, washed and dried.
A kind of preparation method of carboxylate as described above, the drying refer to the vacuum in 25~50 DEG C of vacuum drying oven Dry 6~18h.
The present invention also provides a kind of carboxylate, the carboxylate is solid-state carboxylate, the molecular structure of the carboxylate Formula is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are following one kind:
The R is the long-chain containing functional element that end group is reaction active groups, the reaction active groups be carboxylic acid group, Phosphate, sulfydryl or hydroxyl, the functional element are one of P, S and N, or are the combination of S and N；
Functional element in the carboxylate molecule be the combination of P, N, P and S, the combination of P and N, N and S combination or P with The combination of S and N, the total content of functional element is 8.14~18.32wt% in the carboxylate molecule.
A kind of carboxylate as described above, the end group is that the long-chain containing functional element of reaction active groups is following knot One of structure:
Wherein, n=2,3,4.
A kind of carboxylate as described above, the molecular weight of the carboxylate are 1288~3048g/mol, fusing point is 65~ 125 DEG C, starting thermal decomposition temperature is 340~420 DEG C.
Carboxylate prepared by the present invention is to be made based on reactant polyfunctional group reactivity difference using melt condensation method Solid-state carboxylate, reaction process depends on the multi-functional activity difference of reactant.It is used in first step reaction process Raw material be the phosphorous nitrogenous dicarboxylic acids of dicarboxylic acids or side group of side group, the phosphorous dicarboxylic acids of side group or side group are nitrogenous Two carboxyl-COOH are directly or by methylene-CH in dicarboxylic acids molecule2It is connected with the same tertiary carbon, since side group is phosphorous Unit structure is bigger to generate space steric effect, make in dicarboxylic acids that side group is phosphorous or the nitrogenous dicarboxylic acids molecule of side group Pass through methylene-CH2The reactivity for the carboxyl-COOH connecting with tertiary carbon is higher than the carboxyl-COOH directly connecting with tertiary carbon, In esterification reaction process, methylene-CH is connected2Carboxyl-COOH can prior to the hydroxyl-OH in pentaerythrite occur ester Change reaction, forms ester bond, and due to the phosphorous dicarboxylic acids of side group or mole of the nitrogenous dicarboxylic acids and pentaerythrite of side group Than for 4:1, the two is reacted in the phosphorous nitrogenous dicarboxylic acids of dicarboxylic acids or side group of side group happens is that end capping reaction - OH in the higher-COOH of activity and pentaerythrite stops after reaction, and the end group of the carboxylate of generation is that former side group contains Lower carboxyl-the COOH of reactivity in the nitrogenous dicarboxylic acids molecule of the dicarboxylic acids or side group of phosphorus, the carboxyl-COOH conduct Reaction active groups participate in subsequent reaction.
In second step reaction process, the difunctional organic acid containing functional element is also due to two officials of space steric effect The reactivity that can be rolled into a ball has differences, when the molar ratio of difunctional organic acid and dihydric alcohol containing functional element is 1:1, instead Answer the hydroxyl-OH in the higher functional group of activity and dihydric alcohol that condensation reaction occurs, carboxylate one end of generation is hydroxyl-OH, The other end is the lower functional group of reactivity in the former difunctional organic acid molecule containing functional element；When containing functional element The molar ratio of difunctional organic acid and dihydric alcohol be 1:2 when, the higher functional group of reactivity first with the hydroxyl in dihydric alcohol Condensation reaction occurs for base-OH, and then the lower functional group of reactivity starts that condensation occurs with the hydroxyl-OH in dihydric alcohol instead It answers, the carboxylate both ends of generation are hydroxyl-OH.
In third step reaction process, the product end that is reacted with second step of carboxyl-COOH of the product end group of first step reaction Hydroxyl-OH further occurrence the esterification of base obtains the carboxylate that end group is hydroxyl-OH or other functional groups.
The utility model has the advantages that
1) carboxylate produced by the present invention is solid type carboxylate, and overcome traditional liquid type carboxylate makes as additive The disadvantage of used time existing addition and storage difficulty；
2) carboxylate end group reaction active groups rich in produced by the present invention, can set its molecular structure Meter, as the reaction monomers further reacted, prepares multi-functional compounds；
3) carboxylate molecular weight produced by the present invention is higher (1288~3048g/mol), and is hub-and-spoke configuration, as addition Agent overcomes the problems, such as that small-molecular-weight additive is easy to migrate, durability is poor in use, can be improved the compatibility with polymer；
4) carboxylate produced by the present invention is as functional additive in use, having with polymeric matrix good compatible Property, it, can in the case where additive amount less (being less than 5wt%) since functional element content is higher (8.14~18.32wt%) Reach preferable modified effect；
5) carboxylate produced by the present invention contains multiple functions element, can play good synergistic effect；
6) method of the invention for preparing carboxylate is simple, belongs to melt condensation, will not be to ring without using a large amount of solvent Border has an impact, and is conducive to environmental protection, while reducing solvent recovery cost.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
Examples 1 to 3
A kind of preparation method of carboxylate, steps are as follows:
1) by the phosphorous binary acid of side group [(the own ring -6- base of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha) methyl] fourth Diacid (DDP) and pentaerythrite are mixed with the molar ratio of 4:1, are carried out under conditions of inert nitrogen gas protection and mechanical stirring Fusion esterification reaction, churned mechanically mixing speed are 300rpm, and the temperature of fusion esterification reaction is 180 DEG C, and the reaction time is 1h collects product after reaction, through dissolution, filters and be dried to obtain the DAPER that end group is carboxyl；Reaction equation is as follows:
2) phenyl-phosphonic acid and dihydric alcohol are mixed with the molar ratio of 1:1, catalyst 4- toluenesulfonic acid, phenyl-phosphonic acid is added Molar ratio with catalyst is 1:0.01, and it is anti-to carry out melt condensation under conditions of inert nitrogen gas protection and mechanical stirring It answers, churned mechanically mixing speed is 300rpm, and the temperature of melt condensation reaction is 180 DEG C, and reaction time 1h obtains end group The DADA of hydroxyl；
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert nitrogen gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 300rpm, fusion esterification reaction time be 1h, collect product, through crushing, dissolution, filtering, It washs and dries 6h in 25 DEG C of vacuum drying oven and obtain carboxylate.
Final carboxylate structural formula obtained is as follows:
WhereinStructural formula it is as follows:
Functional element in finally obtained carboxylate molecule is P, when the dihydric alcohol in second step reaction process is
When ethylene glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 4~6
A kind of preparation method of carboxylate, steps are as follows:
1) the nitrogenous binary acid of side group and pentaerythrite are mixed with the molar ratio of 4:1, in inert nitrogen gas protection and machine Fusion esterification reaction is carried out under conditions of tool stirring, churned mechanically mixing speed is 310rpm, the temperature of fusion esterification reaction It is 180 DEG C, reaction time 2h collects product after reaction, through dissolution, filters and is dried to obtain end group as carboxyl DAPER；Reaction equation is as follows:
2) phenyl-phosphonic acid and dihydric alcohol are mixed with the molar ratio of 1:2, catalyst 4- toluenesulfonic acid, phenyl-phosphonic acid is added Molar ratio with catalyst is 1:0.01, and it is anti-to carry out melt condensation under conditions of inert nitrogen gas protection and mechanical stirring It answers, churned mechanically mixing speed is 320rpm, and the temperature of melt condensation reaction is 182 DEG C, and reaction time 1h obtains end group The DADA of hydroxyl；
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert nitrogen gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 330rpm, fusion esterification reaction time be 2h, collect product, through crushing, dissolution, filtering, It washs and dries 7h in 26 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P and N, when the dihydric alcohol in second step reaction process is second When glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 7~9
A kind of preparation method of carboxylate, steps are as follows:
1) the nitrogenous binary acid of side group and pentaerythrite are mixed with the molar ratio of 4:1, in inert nitrogen gas protection and machine Fusion esterification reaction is carried out under conditions of tool stirring, churned mechanically mixing speed is 340rpm, the temperature of fusion esterification reaction It is 182 DEG C, reaction time 3h collects product after reaction, through dissolution, filters and is dried to obtain end group as carboxyl DAPER；Reaction equation is as follows:
2) methylphosphonic acid and dihydric alcohol are mixed with the molar ratio of 1:1, catalyst 4- toluenesulfonic acid, methylphosphonic acid is added Molar ratio with catalyst is 1:0.01, and it is anti-to carry out melt condensation under conditions of inert nitrogen gas protection and mechanical stirring It answers, churned mechanically mixing speed is 350rpm, and the temperature of melt condensation reaction is 183 DEG C, and reaction time 1h obtains end group The DADA of hydroxyl；
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert nitrogen gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 360rpm, fusion esterification reaction time be 2h, collect product, through crushing, dissolution, filtering, It washs and dries 8h in 27 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P and N, when the dihydric alcohol in second step reaction process is second When glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 10~12
A kind of preparation method of carboxylate, steps are as follows:
1) the nitrogenous binary acid of side group and pentaerythrite are mixed with the molar ratio of 4:1, in inert nitrogen gas protection and machine Fusion esterification reaction is carried out under conditions of tool stirring, churned mechanically mixing speed is 370rpm, the temperature of fusion esterification reaction It is 184 DEG C, reaction time 4h collects product after reaction, through dissolution, filters and is dried to obtain end group as carboxyl DAPER；Reaction equation is as follows:
2) methylphosphonic acid and dihydric alcohol are mixed with the molar ratio of 1:2, catalyst 4- toluenesulfonic acid is added, contains Functional Unit The difunctional organic acid of element and the molar ratio of catalyst are 1:0.01, in inert nitrogen gas protection and churned mechanically condition Lower progress melt condensation reaction, churned mechanically mixing speed are 380rpm, and the temperature of melt condensation reaction is 184 DEG C, reaction Time is 2h, obtains the DADA of end group hydroxyl；
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert nitrogen gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 390rpm, fusion esterification reaction time be 3h, collect product, through crushing, dissolution, filtering, It washs and dries 10h in 28 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P and N, when the dihydric alcohol in second step reaction process is second When glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 13~15
A kind of preparation method of carboxylate, steps are as follows:
1) the nitrogenous binary acid of side group and pentaerythrite are mixed with the molar ratio of 4:1, in inert gas argon gas shielded and machine Fusion esterification reaction is carried out under conditions of tool stirring, churned mechanically mixing speed is 400rpm, the temperature of fusion esterification reaction It is 185 DEG C, reaction time 1h collects product after reaction, through dissolution, filters and is dried to obtain end group as carboxyl DAPER；Reaction equation is as follows:
2) 2- carboxyethyl phenyl phosphinic acid and dihydric alcohol are mixed with the molar ratio of 1:1, catalyst 4- methylbenzene sulphur is added The molar ratio of acid, 2- carboxyethyl phenyl phosphinic acid and catalyst is 1:0.01, in inert gas argon gas shielded and churned mechanically Under the conditions of carry out melt condensation reaction, churned mechanically mixing speed be 410rpm, melt condensation reaction temperature be 185 DEG C, Reaction time is 2h, obtains the DADA of end group hydroxyl；
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert gas argon gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 420rpm, fusion esterification reaction time be 3h, collect product, through crushing, dissolution, filtering, It washs and dries 11h in 30 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P and N, when the dihydric alcohol in second step reaction process is second When glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 16~18
A kind of preparation method of carboxylate, steps are as follows:
1) DDP and pentaerythrite are mixed with the molar ratio of 4:1, in inert gas argon gas shielded and churned mechanically condition Lower progress fusion esterification reaction, churned mechanically mixing speed are 430rpm, and the temperature of fusion esterification reaction is 185 DEG C, reaction Time is 2h, collects product after reaction, through dissolution, filters and be dried to obtain the DAPER that end group is carboxyl；
2) 2- carboxyethyl phenyl phosphinic acid and dihydric alcohol are mixed with the molar ratio of 1:2, catalyst 4- methylbenzene sulphur is added The molar ratio of acid, 2- carboxyethyl phenyl phosphinic acid and catalyst is 1:0.01, in inert gas argon gas shielded and churned mechanically Under the conditions of carry out melt condensation reaction, churned mechanically mixing speed be 440rpm, melt condensation reaction temperature be 185 DEG C, Reaction time is 2h, obtains the DADA of end group hydroxyl；
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert gas argon gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 400rpm, fusion esterification reaction time be 4h, collect product, through crushing, dissolution, filtering, It washs and dries 12h in 32 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P, when the dihydric alcohol in second step reaction process is second two When alcohol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 19~21
A kind of preparation method of carboxylate, steps are as follows:
1) DDP and pentaerythrite are mixed with the molar ratio of 4:1, in inert gas argon gas shielded and churned mechanically condition Lower progress fusion esterification reaction, churned mechanically mixing speed are 450rpm, and the temperature of fusion esterification reaction is 186 DEG C, reaction Time is 3h, collects product after reaction, through dissolution, filters and be dried to obtain the DAPER that end group is carboxyl；
2) by [(the own ring -6- base of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha) methyl] succinic acid and dihydric alcohol with The molar ratio of 1:1 mixes, and catalyst 4- toluenesulfonic acid is added, [(6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha oneself Ring -6- base) methyl] molar ratio of succinic acid and catalyst is 1:0.01, in inert gas argon gas shielded and churned mechanically item Melt condensation reaction is carried out under part, churned mechanically mixing speed is 460rpm, and the temperature of melt condensation reaction is 186 DEG C, instead It is 2h between seasonable, obtains the DADA of end group hydroxyl；
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert gas argon gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 470rpm, fusion esterification reaction time be 4h, collect product, through crushing, dissolution, filtering, It washs and dries 13h in 35 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P, when the dihydric alcohol in second step reaction process is second two When alcohol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 22~24
A kind of preparation method of carboxylate, steps are as follows:
1) the nitrogenous binary acid of side group and pentaerythrite are mixed with the molar ratio of 4:1, in inert gas argon gas shielded and machine Fusion esterification reaction is carried out under conditions of tool stirring, churned mechanically mixing speed is 480rpm, the temperature of fusion esterification reaction It is 188 DEG C, reaction time 4h collects product after reaction, through dissolution, filters and is dried to obtain end group as carboxyl DAPER；Reaction equation is as follows:
2) by [(the own ring -6- base of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha) methyl] succinic acid and dihydric alcohol with The molar ratio of 1:2 mixes, and catalyst 4- toluenesulfonic acid is added, [(6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha oneself Ring -6- base) methyl] molar ratio of succinic acid and catalyst is 1:0.01, in inert gas argon gas shielded and churned mechanically item Melt condensation reaction is carried out under part, churned mechanically mixing speed is 490rpm, and the temperature of melt condensation reaction is 187 DEG C, instead It is 3h between seasonable, obtains the DADA of end group hydroxyl；
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert gas argon gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 500rpm, fusion esterification reaction time be 1h, collect product, through crushing, dissolution, filtering, It washs and dries 14h in 36 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P and N, when the dihydric alcohol in second step reaction process is second When glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 25~27
A kind of preparation method of carboxylate, steps are as follows:
1) the nitrogenous binary acid of side group and pentaerythrite are mixed with the molar ratio of 4:1, in inert gas argon gas shielded and machine Fusion esterification reaction is carried out under conditions of tool stirring, churned mechanically mixing speed is 500rpm, the temperature of fusion esterification reaction It is 188 DEG C, reaction time 1h collects product after reaction, through dissolution, filters and is dried to obtain end group as carboxyl DAPER；The structural formula of the nitrogenous binary acid of side group is as follows:
2) nitrogenous dicarboxylic acids and dihydric alcohol are mixed with the molar ratio of 1:1, catalyst 4- toluenesulfonic acid is added, it is nitrogenous The molar ratio of dicarboxylic acids and catalyst is 1:0.01, is melted under conditions of inert gas argon gas shielded and mechanical stirring Condensation reaction, churned mechanically mixing speed are 500rpm, and the temperature of melt condensation reaction is 188 DEG C, and reaction time 3h is obtained To the DADA of end group hydroxyl；The structural formula of nitrogenous dicarboxylic acids is as follows:
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert gas argon gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 500rpm, fusion esterification reaction time be 1h, collect product, through crushing, dissolution, filtering, It washs and dries 15h in 38 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is N, when the dihydric alcohol in second step reaction process is
When ethylene glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 28~30
A kind of preparation method of carboxylate, steps are as follows:
1) the nitrogenous binary acid of side group and pentaerythrite are mixed with the molar ratio of 4:1, in inert gas argon gas shielded and machine Fusion esterification reaction is carried out under conditions of tool stirring, churned mechanically mixing speed is 500rpm, the temperature of fusion esterification reaction It is 190 DEG C, reaction time 2h collects product after reaction, through dissolution, filters and is dried to obtain end group as carboxyl DAPER；The structural formula of the nitrogenous binary acid of side group is as follows:
2) nitrogenous dicarboxylic acids and dihydric alcohol are mixed with the molar ratio of 1:2, catalyst 4- toluenesulfonic acid is added, it is nitrogenous The molar ratio of dicarboxylic acids and catalyst is 1:0.01, is melted under conditions of inert gas argon gas shielded and mechanical stirring Condensation reaction, churned mechanically mixing speed are 500rpm, and the temperature of melt condensation reaction is 189 DEG C, and reaction time 3h is obtained To the DADA of end group hydroxyl；The structural formula of nitrogenous dicarboxylic acids is as follows:
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert gas argon gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 500rpm, fusion esterification reaction time be 2h, collect product, through crushing, dissolution, filtering, It washs and dries 16h in 40 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is N, when the dihydric alcohol in second step reaction process is second two When alcohol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 31~33
A kind of preparation method of carboxylate, steps are as follows:
1) DDP and pentaerythrite are mixed with the molar ratio of 4:1, in inert nitrogen gas protection and churned mechanically condition Lower progress fusion esterification reaction, churned mechanically mixing speed are 300rpm, and the temperature of fusion esterification reaction is 190 DEG C, reaction Time is 3h, collects product after reaction, through dissolution, filters and be dried to obtain the DAPER that end group is carboxyl；
2) nitrogenous dicarboxylic acids and dihydric alcohol are mixed with the molar ratio of 1:1, catalyst 4- toluenesulfonic acid is added, it is nitrogenous The molar ratio of dicarboxylic acids and catalyst is 1:0.01, is melted under conditions of inert nitrogen gas protection and mechanical stirring Condensation reaction, churned mechanically mixing speed are 400rpm, and the temperature of melt condensation reaction is 190 DEG C, and reaction time 3h is obtained To the DADA of end group hydroxyl；The structural formula of nitrogenous dicarboxylic acids is as follows:
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert nitrogen gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 500rpm, fusion esterification reaction time be 2h, collect product, through crushing, dissolution, filtering, It washs and dries 17h in 42 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P and N, when the dihydric alcohol in second step reaction process is second When glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 34~36
A kind of preparation method of carboxylate, steps are as follows:
1) DDP and pentaerythrite are mixed with the molar ratio of 4:1, in inert nitrogen gas protection and churned mechanically condition Lower progress fusion esterification reaction, churned mechanically mixing speed are 500rpm, and the temperature of fusion esterification reaction is 192 DEG C, reaction Time is 4h, collects product after reaction, through dissolution, filters and be dried to obtain the DAPER that end group is carboxyl；
2) nitrogenous dicarboxylic acids and dihydric alcohol are mixed with the molar ratio of 1:2, catalyst 4- toluenesulfonic acid is added, it is nitrogenous The molar ratio of dicarboxylic acids and catalyst is 1:0.01, is melted under conditions of inert nitrogen gas protection and mechanical stirring Condensation reaction, churned mechanically mixing speed are 500rpm, and the temperature of melt condensation reaction is 192 DEG C, and reaction time 1h is obtained To the DADA of end group hydroxyl；The structural formula of nitrogenous dicarboxylic acids is as follows:
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert nitrogen gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 500rpm, fusion esterification reaction time be 3h, collect product, through crushing, dissolution, filtering, It washs and dries 18h in 44 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P and N, when the dihydric alcohol in second step reaction process is second When glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 37~39
A kind of preparation method of carboxylate, steps are as follows:
1) DDP and pentaerythrite are mixed with the molar ratio of 4:1, in inert nitrogen gas protection and churned mechanically condition Lower progress fusion esterification reaction, churned mechanically mixing speed are 400rpm, and the temperature of fusion esterification reaction is 194 DEG C, reaction Time is 1h, collects product after reaction, through dissolution, filters and be dried to obtain the DAPER that end group is carboxyl；
2) nitrogenous dicarboxylic acids and dihydric alcohol are mixed with the molar ratio of 1:1, catalyst 4- toluenesulfonic acid is added, it is nitrogenous The molar ratio of dicarboxylic acids and catalyst is 1:0.01, is melted under conditions of inert nitrogen gas protection and mechanical stirring Condensation reaction, churned mechanically mixing speed are 450rpm, and the temperature of melt condensation reaction is 193 DEG C, and reaction time 1h is obtained To the DADA of end group hydroxyl；The structural formula of nitrogenous dicarboxylic acids is as follows:
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert nitrogen gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 500rpm, fusion esterification reaction time be 3h, collect product, through crushing, dissolution, filtering, It washs and dries 6h in 45 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P and N, when the dihydric alcohol in second step reaction process is second When glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 40~42
A kind of preparation method of carboxylate, steps are as follows:
1) DDP and pentaerythrite are mixed with the molar ratio of 4:1, in inert nitrogen gas protection and churned mechanically condition Lower progress fusion esterification reaction, churned mechanically mixing speed are 300rpm, and the temperature of fusion esterification reaction is 195 DEG C, reaction Time is 2h, collects product after reaction, through dissolution, filters and be dried to obtain the DAPER that end group is carboxyl；
2) nitrogenous dicarboxylic acids and dihydric alcohol are mixed with the molar ratio of 1:2, catalyst 4- toluenesulfonic acid is added, it is nitrogenous The molar ratio of dicarboxylic acids and catalyst is 1:0.01, is melted under conditions of inert nitrogen gas protection and mechanical stirring Condensation reaction, churned mechanically mixing speed are 380rpm, and the temperature of melt condensation reaction is 194 DEG C, and reaction time 2h is obtained To the DADA of end group hydroxyl；The structural formula of nitrogenous dicarboxylic acids is as follows:
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert nitrogen gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 450rpm, fusion esterification reaction time be 4h, collect product, through crushing, dissolution, filtering, It washs and dries 6h in 46 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P and N, when the dihydric alcohol in second step reaction process is second When glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 43~45
A kind of preparation method of carboxylate, steps are as follows:
1) DDP and pentaerythrite are mixed with the molar ratio of 4:1, in inert nitrogen gas protection and churned mechanically condition Lower progress fusion esterification reaction, churned mechanically mixing speed are 460rpm, and the temperature of fusion esterification reaction is 195 DEG C, reaction Time is 3h, collects product after reaction, through dissolution, filters and be dried to obtain the DAPER that end group is carboxyl；
2) by containing S and N monocarboxylic acid and dihydric alcohol mixed with the molar ratio of 1:1, catalyst 4- toluenesulfonic acid is added, The molar ratio of monocarboxylic acid and catalyst containing S and N is 1:0.01, under conditions of inert gas argon gas shielded and mechanical stirring Melt condensation reaction is carried out, churned mechanically mixing speed is 480rpm, and the temperature of melt condensation reaction is 195 DEG C, when reaction Between be 2h, obtain the DADA of end group hydroxyl；Monocarboxylic structural formula containing S and N is as follows:
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert gas argon gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 500rpm, fusion esterification reaction time be 4h, collect product, through crushing, dissolution, filtering, It washs and dries 10h in 48 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P, S and N, when the dihydric alcohol in second step reaction process is When ethylene glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 46~48
A kind of preparation method of carboxylate, steps are as follows:
1) DDP and pentaerythrite are mixed with the molar ratio of 4:1, in inert gas argon gas shielded and churned mechanically condition Lower progress fusion esterification reaction, churned mechanically mixing speed are 400rpm, and the temperature of fusion esterification reaction is 196 DEG C, reaction Time is 4h, collects product after reaction, through dissolution, filters and be dried to obtain the DAPER that end group is carboxyl；
2) organic acid containing S and dihydric alcohol are mixed with the molar ratio of 1:1, catalyst 4- toluenesulfonic acid is added, it is organic containing S The molar ratio of acid and catalyst is 1:0.01, and it is anti-that melt condensation is carried out under conditions of inert gas argon gas shielded and mechanical stirring It answers, churned mechanically mixing speed is 480rpm, and the temperature of melt condensation reaction is 196 DEG C, and reaction time 3h obtains end group The DADA of hydroxyl；The structural formula of the organic acid containing S is as follows:
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert gas argon gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 420rpm, fusion esterification reaction time be 1h, collect product, through crushing, dissolution, filtering, It washs and dries 18h in 50 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P and S, when the dihydric alcohol in second step reaction process is second When glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 49~51
A kind of preparation method of carboxylate, steps are as follows:
1) the nitrogenous binary acid of side group and pentaerythrite are mixed with the molar ratio of 4:1, in inert gas argon gas shielded and machine Fusion esterification reaction is carried out under conditions of tool stirring, churned mechanically mixing speed is 300rpm, the temperature of fusion esterification reaction It is 200 DEG C, reaction time 4h collects product after reaction, through dissolution, filters and is dried to obtain end group as carboxyl DAPER；The structural formula of the nitrogenous binary acid of side group is as follows:
2) by containing S and N dicarboxylic acids and dihydric alcohol mixed with the molar ratio of 1:1, catalyst 4- toluenesulfonic acid is added, The molar ratio of dicarboxylic acids and catalyst containing S and N is 1:0.01, under conditions of inert gas argon gas shielded and mechanical stirring Melt condensation reaction is carried out, churned mechanically mixing speed is 400rpm, and the temperature of melt condensation reaction is 195 DEG C, when reaction Between be 1h, obtain the DADA of end group hydroxyl；The structural formula of dicarboxylic acids containing S and N is as follows:
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert gas argon gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 500rpm, fusion esterification reaction time be 1h, collect product, through crushing, dissolution, filtering, It washs and dries 10h in 50 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is S and N, when the dihydric alcohol in second step reaction process is second When glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.
Embodiment 52~54
A kind of preparation method of carboxylate, steps are as follows:
1) DDP and pentaerythrite are mixed with the molar ratio of 4:1, in inert gas argon gas shielded and churned mechanically condition Lower progress fusion esterification reaction, churned mechanically mixing speed are 300rpm, and the temperature of fusion esterification reaction is 200 DEG C, reaction Time is 4h, collects product after reaction, through dissolution, filters and be dried to obtain the DAPER that end group is carboxyl；
2) by containing S and N dicarboxylic acids and dihydric alcohol mixed with the molar ratio of 1:2, catalyst 4- toluenesulfonic acid is added, The molar ratio of dicarboxylic acids and catalyst containing S and N is 1:0.01, under conditions of inert nitrogen gas protection and mechanical stirring Melt condensation reaction is carried out, churned mechanically mixing speed is 400rpm, and the temperature of melt condensation reaction is 200 DEG C, when reaction Between be 3h, obtain the DADA of end group hydroxyl；The structural formula of dicarboxylic acids containing S and N is as follows:
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1: 4, the temperature-resistant of system is kept, inert nitrogen gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, Churned mechanically mixing speed be 500rpm, fusion esterification reaction time be 2h, collect product, through crushing, dissolution, filtering, It washs and dries 18h in 50 DEG C of vacuum drying oven and obtain carboxylate.
The molecular structural formula of final carboxylate obtained is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate The quaternary carbon C connection of molecular center, concrete structure formula are as follows:
The structural formula of R is specific as follows:
Functional element in finally obtained carboxylate molecule is P, S and N, when the dihydric alcohol in second step reaction process is When ethylene glycol, propylene glycol or butanediol, the value of n and the performance of carboxylate such as following table in carboxylate molecule.

Claims (9)

1. a kind of preparation method of carboxylate, characterized in that the preparation method of the carboxylate is based on reactant polyfunctional group The melt condensation method of reactivity difference, the reactivity difference refer to the polyfunctional group in reactant by steric hindrance Influence that there is different reactivities, according to the sequence of reactivity from high to low condensation reaction occurs for polyfunctional group, and step is such as Under:
1) side group binary acid containing functional element is mixed with pentaerythrite with the molar ratio of 4:1, in inert gas shielding and machinery Fusion esterification reaction is carried out under conditions of stirring, collects product, it is post-treated to obtain the DAPER that end group is carboxyl；The side group In binary acid containing functional element functional element be phosphorus or nitrogen, two acidic-groups of side group binary acid containing functional element it is anti- Active difference is answered, the structural formula of side group binary acid containing functional element is one of following:
2) by containing functional element difunctional organic acid and dihydric alcohol mixed with the molar ratio of 1:1 or 1:2, catalyst is added, Melt condensation reaction is carried out under conditions of inert gas shielding and mechanical stirring, obtains the DADA of end group hydroxyl；It is described to contain Reactivity bifunctional is different in the difunctional organic acid of functional element, and the difunctional is phosphate and carboxylic acid Base, carboxylic acid group and sulfydryl, two carboxylic acid groups or two phosphates, the functional element are one of P, S and N, or for S and The combination of N；
3) DAPER obtained in step 1) is added in the system in step 2), the molar ratio of DAPER and DADA are 1:4, are protected The temperature-resistant of system is held, inert gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical stirring, collects and produces Object, it is post-treated to obtain carboxylate.
2. a kind of preparation method of carboxylate according to claim 1, which is characterized in that in step 1), the indifferent gas Body is argon gas, and the churned mechanically mixing speed is 300~500rpm；The temperature of the fusion esterification reaction is 180~200 DEG C, the reaction time is 1~4h；The post-processing includes dissolution, filtering and drying.
3. a kind of preparation method of carboxylate according to claim 1, which is characterized in that double officials containing functional element It is phenyl-phosphonic acid, methylphosphonic acid, 2- carboxyethyl phenyl phosphinic acid, [(6- oxo -6H- dibenzo [c, e] [1,2] that organic acid, which can be rolled into a ball, Own ring -6- the base of oxygen phospha) methyl] succinic acid or following one of the compound of structural formula:
The dihydric alcohol is ethylene glycol, propylene glycol or 1,4- butanediol.
4. a kind of preparation method of carboxylate according to claim 1, which is characterized in that in step 2), the catalyst For 4- toluenesulfonic acid, the molar ratio of the difunctional organic acid and catalyst containing functional element is 1:0.01, described lazy Property gas be argon gas, the churned mechanically mixing speed is 300~500rpm, and the temperature of melt condensation reaction is 180 ~200 DEG C, the reaction time is 1~3h.
5. a kind of preparation method of carboxylate according to claim 1, which is characterized in that in step 3), the indifferent gas Body is argon gas, and the churned mechanically mixing speed is 300~500rpm, and the time of the fusion esterification reaction is 1~4h, institute Stating post-processing includes crushing, dissolving, being filtered, washed and dried.
6. a kind of preparation method of carboxylate according to claim 5, which is characterized in that the drying refers to 25~50 DEG C vacuum drying oven in 6~18h of vacuum drying.
7. using a kind of carboxylate made from preparation method as described in claim 1, it is characterized in that: the carboxylate is solid-state The molecular structural formula of carboxylate, the carboxylate is as follows:
In formula,Represent the segment between the quaternary carbon C and R of carboxylate the molecular center ,-CH in segment2With carboxylate molecule The quaternary carbon C connection at center, concrete structure formula are following one kind:
The R is the long-chain containing functional element that end group is reaction active groups, and the reaction active groups are carboxylic acid group, phosphoric acid Base, sulfydryl or hydroxyl, the functional element are one of P, S and N, or are the combination of S and N；
Combination, the combination of N and S or the combination of P and S and N that functional element in the carboxylate molecule is P and N, the esterification The total content of functional element is 8.14~18.32wt% in object molecule.
8. a kind of carboxylate according to claim 7, which is characterized in that the end group is reaction active groups containing function The long-chain of element is with one of flowering structure:
Wherein, n=2,3,4.
9. a kind of carboxylate according to claim 7, which is characterized in that the molecular weight of the carboxylate be 1288~ 3048g/mol, fusing point are 65~125 DEG C, and starting thermal decomposition temperature is 340~420 DEG C.
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