CN106866516B - A kind of end group is the organic nitrogen-containing carboxylate and preparation method thereof of carboxylic acid group - Google Patents
A kind of end group is the organic nitrogen-containing carboxylate and preparation method thereof of carboxylic acid group Download PDFInfo
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The present invention relates to the organic nitrogen-containing carboxylates and preparation method thereof that a kind of end group is carboxylic acid group, pass through the DAPER for reacting to obtain end group for carboxyl of the nitrogenous dicarboxylic acids of side group with pentaerythrite first, then react to obtain the DADA that one end is carboxylic acid group, the other end is hydroxyl by organic nitrogen-containing dicarboxylic acids and dihydric alcohol, finally by DAPER and DADA react obtain final products.Preparation method of the invention is based on reactant polyfunctional group reactivity difference, final end group obtained is that the organic nitrogen-containing carboxylate of carboxylic acid group overcomes the storage of traditional liquid type carboxylate and simply leads to the disadvantages of purposes is single, preparation process pollutes environment using difficult, structure, end group is that the organic nitrogen-containing carboxylate of carboxylic acid group is the solid-state carboxylate of high molecular weight, the end group of molecule is carboxylic acid group, nitrogen of the inside containing 12.02~13.21wt% has many advantages, such as that thermal stability is high, widely used.
Description
Technical field
The invention belongs to flame retardant area, it is related to organic nitrogen-containing carboxylate and its preparation side that a kind of end group is carboxylic acid group
Method, in particular to a kind of solid-state end group is for the organic nitrogen-containing carboxylate of carboxylic acid group and its based on reactant polyfunctional group reactivity
The melt condensation preparation method of 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 the organic nitrogen-containing carboxylate that higher solid type end group is carboxylic acid group.
In order to achieve the above objectives, the technical solution adopted by the present invention are as follows:
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and the end group is the organic nitrogen-containing of carboxylic acid group
The preparation method of carboxylate is the melt condensation method based on reactant polyfunctional group reactivity difference, the reactivity difference
Referring to that the polyfunctional group in reactant is influenced by steric hindrance has different reactivities, and polyfunctional group is lived according to reaction
Property sequence from high to low condensation reaction occurs, steps are as follows:
1) the nitrogenous dicarboxylic acids of side group 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
The reactivity of two carboxylic acid groups is different in nitrogenous dicarboxylic acids, the structural formula of the nitrogenous dicarboxylic acids of side group be it is following it
One:
2) organic nitrogen-containing dicarboxylic acids and dihydric alcohol are mixed with the molar ratio of 1:1, catalyst is added, protected in inert gas
Melt condensation reaction is carried out under conditions of shield and mechanical stirring, obtains the DADA that one end is carboxylic acid group, the other end is hydroxyl；It is described
The reactivity of two carboxylic acid groups in organic nitrogen-containing dicarboxylic acids is different；
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 the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
As a preferred technical scheme:
A kind of end group as described above is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, described lazy in step 1)
Property gas be nitrogen or argon gas, the churned mechanically mixing speed be 300~500rpm；The temperature of the fusion esterification reaction
It is 180~200 DEG C, the reaction time is 1~4h；The post-processing includes dissolution, filtering and drying.
A kind of end group as described above is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, the organic nitrogen-containing binary
Carboxylic acid is following one of the compound of structural formula:
The dihydric alcohol is ethylene glycol, propylene glycol or 1,4- butanediol.
A kind of end group as described above is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, described to urge in step 2)
Agent is 4- toluenesulfonic acid, and the molar ratio of the organic nitrogen-containing dicarboxylic acids and catalyst is 1:0.01, the inert gas
For nitrogen or argon gas, the churned mechanically mixing speed is 300~500rpm, and the temperature of the melt condensation reaction is 180
~200 DEG C, the reaction time is 1~3h.
A kind of end group as described above is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, described lazy in step 3)
Property gas be nitrogen or argon gas, the churned mechanically mixing speed is 300~500rpm, the time of fusion esterification reaction
For 1~4h, the post-processing includes crushing, dissolving, being filtered, washed and dried.
A kind of end group as described above is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and the drying refers to 25
6~18h of vacuum drying in~50 DEG C of vacuum drying oven.
The present invention also provides the organic nitrogen-containing carboxylate that a kind of end group is carboxylic acid group, the end group is the organic of carboxylic acid group
Nitrogenous carboxylate is solid-state carboxylate, and the end group is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is following one kind:
The R is the nitrogenous long-chain that end group is carboxylic acid group；
The end group be the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group be 12.02~
13.21wt%.
As a preferred technical scheme:
A kind of end group as described above is the organic nitrogen-containing carboxylate of carboxylic acid group, and the end group is the nitrogenous long-chain of carboxylic acid group
For with one of flowering structure:
Wherein, n=2,3,4.
A kind of end group as described above is the organic nitrogen-containing carboxylate of carboxylic acid group, and the end group is the organic nitrogen-containing of carboxylic acid group
The molecular weight of carboxylate is 1696~1864g/mol, and fusing point is 65~125 DEG C, and 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 end group be carboxylic acid group organic nitrogen-containing carboxylate, reaction process depends on the multi-functional poor activity of reactant
It is different.Raw material used in first step reaction process is the nitrogenous dicarboxylic acids of side group, two carboxylics in the nitrogenous dicarboxylic acids molecule of side group
Base-COOH is directly or by methylene-CH2It is connected with the same tertiary carbon, sky can be generated since side group nitrogen-containing group structure is bigger
Between steric effect, make in the nitrogenous dicarboxylic acids molecule of side group through methylene-CH2The reaction for the carboxyl-COOH being connect with tertiary carbon
Activity is higher than the carboxyl-COOH directly connecting with tertiary carbon, in esterification reaction process, connects methylene-CH2Carboxyl-COOH
Esterification can occur prior to the hydroxyl-OH in pentaerythrite, form ester bond, and due to the nitrogenous dicarboxylic acids of side group and season penta
The molar ratio of tetrol is 4:1, the two happens is that end capping reaction, therefore in the nitrogenous dicarboxylic acids of side group reactivity it is higher-
- OH in COOH and pentaerythrite stops after reaction, and the end group of generation is the end of the organic nitrogen-containing carboxylate of carboxylic acid group
Base is that the lower carboxyl-COOH of reactivity, the carboxyl-COOH are used as reactivity base in the nitrogenous dicarboxylic acids molecule of former side group
Group participates in subsequent reaction.
In second step reaction process, organic nitrogen-containing dicarboxylic acids also due to two carboxylic acid groups of space steric effect reaction
Activity has differences, and when the molar ratio of organic nitrogen-containing dicarboxylic acids and dihydric alcohol is 1:1, reacts in organic nitrogen-containing dicarboxylic acids
Condensation reaction occurs for the hydroxyl-OH in the higher carboxylic acid group of activity and dihydric alcohol, and carboxylate one end of generation is hydroxyl-OH, separately
One end is the lower carboxylic acid group of reactivity in former organic nitrogen-containing dicarboxylic acids molecule.
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 organic nitrogen-containing carboxylate that end group is carboxylic acid group.
The utility model has the advantages that
1) carboxylate produced by the present invention is the organic nitrogen-containing carboxylate that solid type end group is carboxylic acid group, overcomes traditional liquid
The disadvantage of figure carboxylate existing addition and storage difficulty when being used as additive；
2) organic nitrogen-containing carboxylate end group carboxylic acid group rich in produced by the present invention can carry out its molecular structure
Design, as the reaction monomers further reacted, prepares multi-functional compounds；
3) end group produced by the present invention is the higher (1696~1864g/ of organic nitrogen-containing carboxylate molecular weight of carboxylic acid group
Mol), and for hub-and-spoke configuration as additive in use, can be improved the compatibility with polymer small-molecular-weight is overcome to add
The problem that agent is easy to migrate, durability is poor；
4) end group produced by the present invention be carboxylic acid group organic nitrogen-containing carboxylate as functional additive in use, with polymerizeing
Object matrix has good compatibility, since nitrogen element content is higher (12.02~13.21wt%), (is less than additive amount is less
Preferable modified effect can be reached in the case where 5wt%)；
5) method of the invention for preparing the organic nitrogen-containing carboxylate that end group is carboxylic acid group is simple, belongs to melt condensation, is not necessarily to
Using a large amount of solvent, environmental protection will not be conducive to environmental effects, while reduce 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.
Embodiment 1
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 300rpm, fusion esterification reaction temperature be 180
DEG C, reaction time 1h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and ethylene glycol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid, You Jihan is added
The molar ratio of nitrogen dicarboxylic acids and 4- toluenesulfonic acid is 1:0.01, is melted under conditions of nitrogen protection and mechanical stirring
Condensation reaction, churned mechanically mixing speed are 300rpm, and the temperature of melt condensation reaction is 180 DEG C, and reaction time 1h is obtained
To the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 300rpm, fusion esterification reaction time be 1h, collect product, through crushing, dissolve, be filtered, washed and
6h is dried in 25 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=2.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
12.79wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1752g/mol, and fusing point is 65 DEG C, starting heat point
Solving temperature is 400 DEG C.
Embodiment 2
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 320rpm, fusion esterification reaction temperature be 181
DEG C, reaction time 1h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and propylene glycol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid, You Jihan is added
The molar ratio of nitrogen dicarboxylic acids and 4- toluenesulfonic acid is 1:0.01, is melted under conditions of nitrogen protection and mechanical stirring
Condensation reaction, churned mechanically mixing speed are 320rpm, and the temperature of melt condensation reaction is 181 DEG C, and reaction time 1h is obtained
To the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 320rpm, fusion esterification reaction time be 1h, collect product, through crushing, dissolve, be filtered, washed and
7h is dried in 27 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=3.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
12.39wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1808g/mol, and fusing point is 70 DEG C, starting heat point
Solving temperature is 385 DEG C.
Embodiment 3
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 345rpm, fusion esterification reaction temperature be 183
DEG C, reaction time 1h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and 1,4-butanediol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid is added, has
The molar ratio of the nitrogenous dicarboxylic acids of machine and 4- toluenesulfonic acid is 1:0.01, is carried out under conditions of nitrogen protection and mechanical stirring
Melt condensation reaction, churned mechanically mixing speed are 345rpm, and the temperature of melt condensation reaction is 183 DEG C, and the reaction time is
1h obtains the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 345rpm, fusion esterification reaction time be 2h, collect product, through crushing, dissolve, be filtered, washed and
8h is dried in 29 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=4.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
12.02wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1864g/mol, and fusing point is 75 DEG C, starting heat point
Solving temperature is 340 DEG C.
Embodiment 4
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 367rpm, fusion esterification reaction temperature be 185
DEG C, reaction time 2h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and ethylene glycol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid, You Jihan is added
The molar ratio of nitrogen dicarboxylic acids and 4- toluenesulfonic acid is 1:0.01, is melted under conditions of nitrogen protection and mechanical stirring
Condensation reaction, churned mechanically mixing speed are 367rpm, and the temperature of melt condensation reaction is 185 DEG C, and reaction time 1h is obtained
To the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 367rpm, fusion esterification reaction time be 2h, collect product, through crushing, dissolve, be filtered, washed and
10h is dried in 30 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=2.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
13.21wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1696g/mol, and fusing point is 80 DEG C, starting heat point
Solving temperature is 420 DEG C.
Embodiment 5
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 383rpm, fusion esterification reaction temperature be 187
DEG C, reaction time 2h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and propylene glycol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid, You Jihan is added
The molar ratio of nitrogen dicarboxylic acids and 4- toluenesulfonic acid is 1:0.01, is melted under conditions of nitrogen protection and mechanical stirring
Condensation reaction, churned mechanically mixing speed are 383rpm, and the temperature of melt condensation reaction is 187 DEG C, and reaction time 2h is obtained
To the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 383rpm, fusion esterification reaction time be 2h, collect product, through crushing, dissolve, be filtered, washed and
11h is dried in 31 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=3.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
12.79wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1752g/mol, and fusing point is 85 DEG C, starting heat point
Solving temperature is 409 DEG C.
Embodiment 6
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 400rpm, fusion esterification reaction temperature be 188
DEG C, reaction time 3h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and propylene glycol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid, You Jihan is added
The molar ratio of nitrogen dicarboxylic acids and 4- toluenesulfonic acid is 1:0.01, is melted under conditions of nitrogen protection and mechanical stirring
Condensation reaction, churned mechanically mixing speed are 400rpm, and the temperature of melt condensation reaction is 188 DEG C, and reaction time 2h is obtained
To the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 400rpm, fusion esterification reaction time be 3h, collect product, through crushing, dissolve, be filtered, washed and
12h is dried in 33 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=4.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
12.39wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1808g/mol, and fusing point is 92 DEG C, starting heat point
Solving temperature is 410 DEG C.
Embodiment 7
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 410rpm, fusion esterification reaction temperature be 190
DEG C, reaction time 3h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and ethylene glycol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid, You Jihan is added
The molar ratio of nitrogen dicarboxylic acids and 4- toluenesulfonic acid is 1:0.01, is melted under conditions of nitrogen protection and mechanical stirring
Condensation reaction, churned mechanically mixing speed are 410rpm, and the temperature of melt condensation reaction is 190 DEG C, and reaction time 2h is obtained
To the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 410rpm, fusion esterification reaction time be 3h, collect product, through crushing, dissolve, be filtered, washed and
13h is dried in 35 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=2.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
13.21wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1696g/mol, and fusing point is 97 DEG C, starting heat point
Solving temperature is 420 DEG C.
Embodiment 8
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 425rpm, fusion esterification reaction temperature be 192
DEG C, reaction time 3h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and propylene glycol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid, You Jihan is added
The molar ratio of nitrogen dicarboxylic acids and 4- toluenesulfonic acid is 1:0.01, is melted under conditions of nitrogen protection and mechanical stirring
Condensation reaction, churned mechanically mixing speed are 425rpm, and the temperature of melt condensation reaction is 192 DEG C, and reaction time 2h is obtained
To the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 425rpm, fusion esterification reaction time be 3h, collect product, through crushing, dissolve, be filtered, washed and
14h is dried in 38 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=3.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
12.79wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1752g/mol, and fusing point is 102 DEG C, starting heat
Decomposition temperature is 405 DEG C.
Embodiment 9
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 444rpm, fusion esterification reaction temperature be 194
DEG C, reaction time 4h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and 1,4-butanediol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid is added, has
The molar ratio of the nitrogenous dicarboxylic acids of machine and 4- toluenesulfonic acid is 1:0.01, is carried out under conditions of nitrogen protection and mechanical stirring
Melt condensation reaction, churned mechanically mixing speed are 444rpm, and the temperature of melt condensation reaction is 194 DEG C, and the reaction time is
3h obtains the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 444rpm, fusion esterification reaction time be 4h, collect product, through crushing, dissolve, be filtered, washed and
15h is dried in 42 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=4.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
12.39wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1808g/mol, and fusing point is 108 DEG C, starting heat
Decomposition temperature is 386 DEG C.
Embodiment 10
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 458rpm, fusion esterification reaction temperature be 196
DEG C, reaction time 4h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and ethylene glycol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid, You Jihan is added
The molar ratio of nitrogen dicarboxylic acids and 4- toluenesulfonic acid is 1:0.01, is melted under conditions of nitrogen protection and mechanical stirring
Condensation reaction, churned mechanically mixing speed are 458rpm, and the temperature of melt condensation reaction is 196 DEG C, and reaction time 3h is obtained
To the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 458rpm, fusion esterification reaction time be 4h, collect product, through crushing, dissolve, be filtered, washed and
16h is dried in 43 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=2.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
12.79wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1752g/mol, and fusing point is 113 DEG C, starting heat
Decomposition temperature is 412 DEG C.
Embodiment 11
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 469rpm, fusion esterification reaction temperature be 197
DEG C, reaction time 4h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and propylene glycol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid, You Jihan is added
The molar ratio of nitrogen dicarboxylic acids and 4- toluenesulfonic acid is 1:0.01, is melted under conditions of nitrogen protection and mechanical stirring
Condensation reaction, churned mechanically mixing speed are 469rpm, and the temperature of melt condensation reaction is 197 DEG C, and reaction time 3h is obtained
To the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 469rpm, fusion esterification reaction time be 4h, collect product, through crushing, dissolve, be filtered, washed and
17h is dried in 46 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=3.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
12.39wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1808g/mol, and fusing point is 118 DEG C, starting heat
Decomposition temperature is 397 DEG C.
Embodiment 12
A kind of end group is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, and steps are as follows:
1) the nitrogenous dicarboxylic acids of side group and pentaerythrite are mixed with the molar ratio of 4:1, in nitrogen protection and mechanical stirring
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed be 500rpm, fusion esterification reaction temperature be 200
DEG C, reaction time 4h collects product after reaction, through dissolution, the DAPER that end group is carboxyl is filtered and is dried to obtain,
The structural formula of the middle nitrogenous dicarboxylic acids of side group are as follows:
2) organic nitrogen-containing dicarboxylic acids and 1,4-butanediol are mixed with the molar ratio of 1:1,4- toluenesulfonic acid is added, has
The molar ratio of the nitrogenous dicarboxylic acids of machine and 4- toluenesulfonic acid is 1:0.01, is carried out under conditions of nitrogen protection and mechanical stirring
Melt condensation reaction, churned mechanically mixing speed are 500rpm, and the temperature of melt condensation reaction is 200 DEG C, and the reaction time is
3h obtains the DADA that one end is carboxylic acid group, the other end is hydroxyl, wherein organic nitrogen-containing dicarboxylic acids structural formula are 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, argon gas is continually fed into, fusion esterification reaction, mechanical stirring are carried out under conditions of mechanical stirring
Mixing speed be 500rpm, fusion esterification reaction time be 4h, collect product, through crushing, dissolve, be filtered, washed and
18h is dried in 50 DEG C of vacuum drying oven obtains the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
Final end group obtained is that the molecular structural formula of the organic nitrogen-containing carboxylate of carboxylic acid group is as follows:
In formula,Segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group is represented,
- CH in segment2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows:
The structural formula of R is specific as follows:
Wherein, n=4.
Finally obtained end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is
12.02wt%, end group are that the molecular weight of the organic nitrogen-containing carboxylate of carboxylic acid group is 1864g/mol, and fusing point is 125 DEG C, starting heat
Decomposition temperature is 340 DEG C.
Claims (7)
1. the preparation method that a kind of end group is the organic nitrogen-containing carboxylate of carboxylic acid group, characterized in that the end group is carboxylic acid group's
The preparation method of organic nitrogen-containing carboxylate is the melt condensation method based on reactant polyfunctional group reactivity difference, the reaction
Activity difference refers to that the polyfunctional group in reactant is influenced to have different reactivities by steric hindrance, and polyfunctional group is pressed
Condensation reaction occurs according to the sequence of reactivity from high to low, steps are as follows:
1) the nitrogenous dicarboxylic acids of side group is mixed with pentaerythrite with the molar ratio of 4:1, in inert gas shielding and mechanical stirring
Under conditions of carry out fusion esterification reaction, collect product, it is post-treated obtain end group be carboxyl DAPER；The side group is nitrogenous
The reactivity of two carboxylic acid groups is different in dicarboxylic acids, and the structural formula of the nitrogenous dicarboxylic acids of side group is one of following:
2) organic nitrogen-containing dicarboxylic acids and dihydric alcohol are mixed with the molar ratio of 1:1, catalyst are added, in inert gas shielding and
Melt condensation reaction is carried out under conditions of mechanical stirring, obtains the DADA that one end is carboxylic acid group, the other end is hydroxyl；It is described organic
The reactivity of two carboxylic acid groups in nitrogenous dicarboxylic acids is different；The organic nitrogen-containing dicarboxylic acids is the following change of structural formula
Close one of object:
The dihydric alcohol is ethylene glycol, propylene glycol or 1,4- butanediol；
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 the organic nitrogen-containing carboxylate that end group is carboxylic acid group.
2. a kind of end group according to claim 1 is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, feature exists
In in step 1), the inert gas is argon gas, and the churned mechanically mixing speed is 300~500rpm；The melting ester
The temperature for changing reaction is 180~200 DEG C, and the reaction time is 1~4h；The post-processing includes dissolution, filtering and drying.
3. a kind of end group according to claim 1 is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, feature exists
In in step 2), the catalyst is 4- toluenesulfonic acid, and the molar ratio of the organic nitrogen-containing dicarboxylic acids and catalyst is 1:
0.01, the inert gas is argon gas, and the churned mechanically mixing speed is 300~500rpm, the melt condensation reaction
Temperature be 180~200 DEG C, the reaction time be 1~3h.
4. a kind of end group according to claim 1 is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, feature exists
In in step 3), the inert gas is argon gas, and the churned mechanically mixing speed is 300~500rpm, the melting ester
The time for changing reaction is 1~4h, and the post-processing includes crushing, dissolving, being filtered, washed and dried.
5. a kind of end group according to claim 4 is the preparation method of the organic nitrogen-containing carboxylate of carboxylic acid group, feature exists
In the drying refers to 6~18h of vacuum drying in 25~50 DEG C of vacuum drying oven.
6. using a kind of end group made from preparation method as claimed in any one of claims 1 to 5 for the organic nitrogen-containing of carboxylic acid group
Carboxylate, it is characterized in that: the organic nitrogen-containing carboxylate that the end group is carboxylic acid group is solid-state carboxylate, the end group is carboxylic acid group
Organic nitrogen-containing carboxylate molecular structural formula it is as follows:
In formula,Represent segment of the end group between the quaternary carbon C and R of the organic nitrogen-containing carboxylate molecular center of carboxylic acid group, segment
In-CH2It is connect with the quaternary carbon C of carboxylate molecular center, concrete structure formula is following one kind:
The R is the nitrogenous long-chain that end group is carboxylic acid group；
The end group is that the total content of nitrogen in the organic nitrogen-containing carboxylate molecule of carboxylic acid group is 12.02~13.21wt%；
The end group is that the nitrogenous long-chain of carboxylic acid group is with one of flowering structure:
Wherein, n=2,3,4.
7. the organic nitrogen-containing carboxylate that a kind of end group according to claim 6 is carboxylic acid group, which is characterized in that the end group
Molecular weight for the organic nitrogen-containing carboxylate of carboxylic acid group is 1696~1864, and fusing point is 65~125 DEG C, and starting thermal decomposition temperature is
340~420 DEG C.
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| WO2008132111A1 (en) * | 2007-04-26 | 2008-11-06 | Basf Se | Flame-retardant thermoplastic molding compositions |
| CN104428357A (en) * | 2012-07-09 | 2015-03-18 | 朗盛德国有限责任公司 | Siliceous rubber mixtures containing omega-mercaptocarboxylic acid ester of polyvalent alcohols |
| CN104861165A (en) * | 2015-06-03 | 2015-08-26 | 宁波工程学院 | Preparation method of mercapto-alkene polymer flame-retardant system |
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| WO2008132111A1 (en) * | 2007-04-26 | 2008-11-06 | Basf Se | Flame-retardant thermoplastic molding compositions |
| CN104428357A (en) * | 2012-07-09 | 2015-03-18 | 朗盛德国有限责任公司 | Siliceous rubber mixtures containing omega-mercaptocarboxylic acid ester of polyvalent alcohols |
| CN104861165A (en) * | 2015-06-03 | 2015-08-26 | 宁波工程学院 | Preparation method of mercapto-alkene polymer flame-retardant system |
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