CN106810579A - A kind of organic phosphorus-nitrogen containing carboxylate of terminal hydroxy group and preparation method thereof and obtained fire-retardant polyester fibre FDY by its - Google Patents
A kind of organic phosphorus-nitrogen containing carboxylate of terminal hydroxy group and preparation method thereof and obtained fire-retardant polyester fibre FDY by its Download PDFInfo
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- CN106810579A CN106810579A CN201710033590.1A CN201710033590A CN106810579A CN 106810579 A CN106810579 A CN 106810579A CN 201710033590 A CN201710033590 A CN 201710033590A CN 106810579 A CN106810579 A CN 106810579A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
- C07F9/6564—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
- C07F9/657172—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 the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
Abstract
The present invention relates to organic phosphorus-nitrogen containing carboxylate of a kind of terminal hydroxy group and preparation method thereof and obtained fire-retardant polyester fibre FDY by its, the DAPER that end group is carboxyl is obtained by side base dicarboxylic acids containing functional element and the reaction of pentaerythrite first, then the DADA that end group is hydroxyl is obtained by organic binary acid containing functional element and the reaction of dihydroxylic alcohols, final products is obtained finally by the reaction of DAPER and DADA.Final products are the solid-state carboxylate of HMW, and the end group of molecule is hydroxyl, P elements of the inside containing 8.48~15.53wt% and nitrogen, has the advantages that heat endurance is high, widely used.Final products are used to as fire retardant to prepare fire-retardant polyester fibre FDY, limited oxygen index >=35% of final obtained fire-retardant polyester fibre FDY, filament number is 3.0~5.0dtex, fracture strength >=3.8cN/dtex.
Description
Technical field
The invention belongs to flame retardant area, be related to organic containing phosphorus-nitrogen carboxylate of a kind of terminal hydroxy group and preparation method thereof and by
Its obtained fire-retardant polyester fibre FDY, more particularly to a kind of organic containing phosphorus-nitrogen carboxylate of solid-state terminal hydroxy group and its based on reaction
The melt condensation preparation method of thing polyfunctional group reactivity difference.
Background technology
With the development and the continuous expansion of application field of China's synthetic material industry, 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, and very big threat is caused to safety of life and property.Therefore, the fire-retardant of polymeric material turns into one
Individual problem demanding prompt solution.The widely used mode for adding fire retardant of all kinds of polymer is improving the fire resistance of material at present.
The advantages of phosphorus flame retardant is with its efficient, low toxicity, environmental protection, obtains the widely studied of domestic and international experts and scholars.
One kind (miscellaneous -10- of 9,10- dihydro-9-oxies containing DOPO that Chinese patent application publication number CN 101880395A are proposed
Phospho hetero phenanthrene -10- oxides) polymer type phosphor-containing fire retardant and preparation method thereof, the aromatic radical dihydric phenol being modified using DOPO
Or aromatic radical dihydroxylic alcohols and dichloride substitution phosphate are that reactant obtains polymer type phosphor-containing fire retardant, but the fire retardant is phosphorous
Amount is relatively low, and addition reaches 15% and can be only achieved preferable fire resistance during use.CN1563152A is changed using DOPO
Property hydroquinones or dichloro (bromine) the oxygen phosphorus of naphthalenediol, phenyl or naphthyl substitution is contained obtaining polymer-type for response matrix
Precipitating reagent large usage quantity in phosphorus fire retardant, but the separation process of the fire retardant, environmental pollution is larger.CN102304230A is used
Double (4- hydroxyphenyls) fluorenes of 9,9- and diphenylphosphoryl dichloro or phenoxy group phosphinylidyne dichloro are that response matrix prepares the phosphorous resistance with fluorenyl
Combustion agent, but its course of reaction is complex, and whard to control and solvent needed for experiment need to be removed water strictly.
In sum, fire retardant at present on the market is mostly that preparation process is deposited obtained in the method by polymerisation in solution
The problems such as complex process, big organic solvent usage amount, difficult solvent recovery and pollution environment, cause to produce and process cost mistake
It is high；The content of functional element (P, N, S etc.) is relatively low in flame retardant molecule, causes the flame retarding efficiency of fire retardant relatively low, it is necessary to larger
Fire retardant addition can be only achieved preferable flame retardant effect, the addition of fire retardant is larger and is easily caused cost raising, right
The other performance of material exerts an adverse impact；Fire retardant is generally small-molecular-weight liquefied compound, the molecule of one side fire retardant
Amount is relatively low to cause that the compatibility between fire retardant and high molecular polymer is poor, and fire retardant is easily reunited in polymeric matrix,
Dispersion is uneven, and migration problem is there is also in use, causes the poor durability of fire-retardant product；Another aspect liquid-type
Fire retardant all has difficulties at aspects such as transport, storage and processing.
Therefore, it is obtained that functional element content is higher and the relatively large solid type of molecular weight is fire-retardant using solvent-free method
Agent has very important significance.
The content of the invention
The purpose of the present invention is to overcome traditional liquid type carboxylate to store and pollute environment, work(using difficult, preparation process
Can constituent content be relatively low, the shortcomings of molecular weight is relatively low, prepares a kind of preparation process less pollution, functional element content higher and divide
The son amount organic containing phosphorus-nitrogen carboxylate of solid type terminal hydroxy group higher.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, the system of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group
Preparation Method is the melt condensation method based on reactant polyfunctional group reactivity difference, and the reactivity difference refers to reactant
In polyfunctional group by steric hindrance influenceed have different reactivities, polyfunctional group according to reactivity from high to low
Order there is condensation reaction, step is as follows：
1) by side base dicarboxylic acids containing functional element and pentaerythrite with 4:1 mixed in molar ratio, in inert gas shielding
With carry out fusion esterification reaction under conditions of mechanical agitation, collect product, it is post-treated to obtain the DAPER that end group is carboxyl；Institute
Functional element is phosphorus or nitrogen, two carboxylics of the side base containing functional element dicarboxylic acids in stating side base dicarboxylic acids containing functional element
The reactivity of acidic group is different, and structural formula of the side base containing functional element dicarboxylic acids is one of following：
2) by organic binary acid containing functional element and dihydroxylic alcohols with 1:2 mixed in molar ratio, adds catalyst, in indifferent gas
Body is protected carries out melt condensation reaction with conditions of mechanical agitation, obtains the DADA that end group is hydroxyl；It is described organic containing function
Functional element in element binary acid is phosphorus or nitrogen, the function in the functional element and the side base dicarboxylic acids containing functional element
Element is different, and the reactivity of two acidic-groups in organic binary acid containing functional element is different, described two acidity
Group is two carboxylic acid groups or phosphate and carboxylic acid group；
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 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 agitation, collect
Product, it is post-treated to obtain the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
As preferred technical scheme：
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group as described above, step 1) in, the inert gas
It is nitrogen or argon gas, 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 dissolving, filtering and dries.
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group as described above, it is described organic containing functional element two
First acid is phenyl-phosphonic acid, methylphosphonic acid, 2- carboxyethyl phenyl phosphinic acids, [(6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha
Own ring -6- bases) methyl] one of succinic acid or the following compound of structural formula：
The dihydroxylic alcohols is ethylene glycol, propane diols or 1,4- butanediols.
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group as described above, step 2) in, the catalyst is
4- toluene sulfonic acides, organic binary acid containing functional element is 1 with the mol ratio of catalyst:0.01, the inert gas is
Nitrogen or argon gas, the churned mechanically mixing speed is 300~500rpm, the temperature of melt condensation reaction for 180~
200 DEG C, the reaction time is 1~3h.
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group as described above, step 3) in, the inert gas
Be nitrogen or argon gas, the churned mechanically mixing speed is 300~500rpm, time of the fusion esterification reaction for 1~
4h, the post processing includes crushing, dissolving, being filtered, washed and dried.
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group as described above, the drying refers to 25~50
DEG C vacuum drying oven in 6~18h of vacuum drying.
Present invention also offers a kind of organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group
It is solid-state carboxylate, the molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected with the quaternary carbon C of carboxylate molecular center, concrete structure formula is following one kind：
The R is that end group is the long-chain containing functional element of hydroxyl, wherein, functional element is phosphorus or nitrogen；
In the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group the total content of P elements and nitrogen be 8.48~
15.53wt%.
As preferred technical scheme：
A kind of organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group as described above, the end group is the long-chain containing functional element of hydroxyl
It is one of following structure：
Wherein, n=2,3,4.
A kind of organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group as described above, the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group point
Son amount is 1520~2784g/mol, and fusing point is 65~125 DEG C, and initial heat decomposition temperature is 340~420 DEG C.
One kind fire-retardant polyester fibre FDY, fire-retardant polyester fibre FDY as obtained in the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group
The preparation process of silk is as follows：
(1) melt blending, the organic containing phosphorus-nitrogen carboxylate of dried terminal hydroxy group and PET sections be mixed to get pre-
Batch mixing, flame retardant polyester section is obtained by being cut into slices after premix melt blending；
(2) melt spinning, the section of dried flame retardant polyester is through measuring, extruding, cool down, oil, stretch, thermal finalization and volume
Around prepared fire-retardant polyester fibre FDY.
Fire-retardant polyester fibre FDY as described above, the melt blending is being carried out in double screw extruder, described molten
The organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group and the mass ratio of PET sections are 3~10 when melting blending:90~97, the melt blending
Temperature is 255~265 DEG C；
The technological parameter of the melt spinning is：
Extrusion temperature：285~300 DEG C；
Chilling temperature：20~25 DEG C；
Network pressure：0.20~0.30MPa；
One roller speed：2200~2600m/min；
One roll temperature：75~90 DEG C；
Two roller speeds：3600~3900m/min；
Two roll temperatures：115~135 DEG C；
Winding speed：4000~4600m/min；
Limited oxygen index >=35% of described fire-retardant polyester fibre FDY, filament number is 3.0~5.0dtex, and fracture is strong
Degree >=3.8cN/dtex, elongation at break is 33.0 ± 3.0%.
Carboxylate prepared by the present invention is, based on reactant polyfunctional group reactivity difference, to be obtained using melt condensation method
The organic containing phosphorus-nitrogen carboxylate of solid-state terminal hydroxy group, course of reaction depends on the multi-functional activity difference of reactant.First
The raw material used in step course of reaction is side base dicarboxylic acids containing functional element, two in side base dicarboxylic acids containing functional element molecule
Individual carboxyl-COOH is directly or by methylene-CH2- be connected with same tertiary carbon, due to side base unit structure containing functional element compared with
Conference produces space steric effect, makes to pass through methylene-CH in side base dicarboxylic acids containing functional element molecule2- be connected with tertiary carbon
The reactivity of carboxyl-COOH be higher than the carboxyl-COOH that directly be connected with tertiary carbon, in esterification reaction process, connection methylene
Base-CH2- carboxyl-COOH esterification can occur prior to the hydroxyl-OH in pentaerythrite, ester bond is formed, and due to side base
Dicarboxylic acids containing functional element is 4 with the mol ratio of pentaerythrite:1, the two happens is that end capping reaction, therefore side base contains function
- OH reactions in element dicarboxylic acids in reactivity-COOH higher and pentaerythrite stop after terminating, the end hydroxyl of generation
The end group of the organic containing phosphorus-nitrogen carboxylate of base be the relatively low carboxyl of reactivity in former side base dicarboxylic acids containing functional element molecule-
COOH, the carboxyl-COOH is participated in follow-up reaction as reaction active groups.
In second step course of reaction, organic binary acid containing functional element is also due to space steric effect Liang Ge functional groups
The reactivity of (acidic-group) has differences, when the mol ratio of organic binary acid containing functional element and dihydroxylic alcohols is 1:When 2, instead
Answer activity functional group's (acidic-group) higher that condensation reaction occurs with the hydroxyl-OH in dihydroxylic alcohols first, then reactivity
Relatively low functional group's (acidic-group) starts that condensation reaction occurs with the hydroxyl-OH in dihydroxylic alcohols, and the carboxylate two ends of generation are
Hydroxyl-OH.
During three-step reaction, the product end of carboxyl-COOH and the second step reaction of the product end group that the first step is reacted
Further there is esterification in the hydroxyl-OH of base, obtain the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
Beneficial effect：
1) the obtained carboxylate of the present invention is the organic containing phosphorus-nitrogen carboxylate of solid type terminal hydroxy group, overcomes traditional liquid type
The addition existed when carboxylate is used as additive and the difficult shortcoming of storage；
2) the obtained organic containing phosphorus-nitrogen carboxylate end group of the present invention contains abundant hydroxyl, and its molecular structure can be entered
Row design, as the reaction monomers of further reaction, prepares multi-functional compounds；
3) the organic containing phosphorus-nitrogen carboxylate molecular weight of the obtained terminal hydroxy group of the present invention is (1520~2784g/mol) higher, and is
Hub-and-spoke configuration, when being used as additive, it is possible to increase the compatibility with polymer, overcome small-molecular-weight additive easily to migrate,
The problem of poor durability；
4) when the obtained organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group of the present invention is used as functional additive, with polymer matrix
Body has good compatibility, less in addition because P elements and nitrogen element content are (8.48~15.53wt%) higher
Preferable modified effect can be reached in the case of (being less than 5wt%)；
5) the organic containing phosphorus-nitrogen carboxylate of the obtained terminal hydroxy group of the present invention not only containing P elements but also contained nitrogen, Neng Gouqi
To good synergy；
6) method for preparing the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group of the invention is simple, belongs to melt condensation, without using big
Environmental effects will not be conducive to environmental protection by the solvent of amount, 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
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
Embodiment 1
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the nitrogenous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in nitrogen protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 300rpm, and the temperature of fusion esterification reaction is 180
DEG C, the reaction time is 1h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle nitrogenous dicarboxylic acids of side base is：
2) by phenyl-phosphonic acid and ethylene glycol with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, phenyl-phosphonic acid and 4- first
The mol ratio of base benzene sulfonic acid is 1:0.01, melt condensation reaction is carried out under conditions of nitrogen protection and mechanical agitation, machinery is stirred
The mixing speed mixed is 300rpm, and the temperature of melt condensation reaction is 180 DEG C, and the reaction time is 1h, and it is hydroxyl to obtain end group
DADA；
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, nitrogen is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 300rpm, fusion esterification reaction time be 1h, collect product, it is size-reduced, dissolving, filtering, washing and
6h is dried in 25 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
13.53wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 1744g/mol, and fusing point is 65 DEG C, starting thermal decomposition temperature
Spend is 395 DEG C.
Embodiment 2
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the nitrogenous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in nitrogen protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 320rpm, and the temperature of fusion esterification reaction is 182
DEG C, the reaction time is 1h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle nitrogenous dicarboxylic acids of side base is：
2) by phenyl-phosphonic acid and propane diols with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, phenyl-phosphonic acid and 4- first
The mol ratio of base benzene sulfonic acid is 1:0.01, melt condensation reaction is carried out under conditions of nitrogen protection and mechanical agitation, machinery is stirred
The mixing speed mixed is 320rpm, and the temperature of melt condensation reaction is 182 DEG C, and the reaction time is 1h, and it is hydroxyl to obtain end group
DADA；
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, nitrogen is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 320rpm, fusion esterification reaction time be 1h, collect product, it is size-reduced, dissolving, filtering, washing and
7h is dried in 26 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
12.72wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 1856g/mol, and fusing point is 69 DEG C, starting thermal decomposition temperature
Spend is 387 DEG C.
Embodiment 3
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the nitrogenous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in nitrogen protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 345rpm, and the temperature of fusion esterification reaction is 184
DEG C, the reaction time is 2h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle nitrogenous dicarboxylic acids of side base is：
2) by methylphosphonic acid and 1,4- butanediols with 1:2 mixed in molar ratio, add 4- toluene sulfonic acides, methylphosphonic acid with
The mol ratio of 4- toluene sulfonic acides is 1:0.01, carry out melt condensation reaction, machine under conditions of argon gas protection and mechanical agitation
The mixing speed of tool stirring is 345rpm, and the temperature of melt condensation reaction is 184 DEG C, and the reaction time is 1h, obtains end group for hydroxyl
The DADA of base；
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, argon gas is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 345rpm, fusion esterification reaction time be 2h, collect product, it is size-reduced, dissolving, filtering, washing and
8h is dried in 28 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
13.53wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 1744g/mol, and fusing point is 73 DEG C, starting thermal decomposition temperature
Spend is 392 DEG C.
Embodiment 4
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the nitrogenous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in argon gas protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 367rpm, and the temperature of fusion esterification reaction is 186
DEG C, the reaction time is 2h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle nitrogenous dicarboxylic acids of side base is：
2) by methylphosphonic acid and ethylene glycol with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, methylphosphonic acid and 4- first
The mol ratio of base benzene sulfonic acid is 1:0.01, melt condensation reaction is carried out under conditions of argon gas protection and mechanical agitation, machinery is stirred
The mixing speed mixed is 367rpm, and the temperature of melt condensation reaction is 186 DEG C, and the reaction time is 2h, and it is hydroxyl to obtain end group
DADA；
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, argon gas is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 367rpm, fusion esterification reaction time be 2h, collect product, it is size-reduced, dissolving, filtering, washing and
9h is dried in 30 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
15.53wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 1520g/mol, and fusing point is 77 DEG C, starting thermal decomposition temperature
Spend is 420 DEG C.
Embodiment 5
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the nitrogenous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in argon gas protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 383rpm, and the temperature of fusion esterification reaction is 188
DEG C, the reaction time is 3h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle nitrogenous dicarboxylic acids of side base is：
2) by 2- carboxyethyl phenyl phosphinic acids and propane diols with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, 2- carboxylics
Ethylphenyl phosphinic acids are 1 with the mol ratio of 4- toluene sulfonic acides:0.01, carried out under conditions of nitrogen protection and mechanical agitation
Melt condensation reacts, and churned mechanically mixing speed is 383rpm, and the temperature of melt condensation reaction is 188 DEG C, and the reaction time is
2h, obtains the DADA that end group is hydroxyl；
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, nitrogen is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 383rpm, fusion esterification reaction time be 3h, collect product, it is size-reduced, dissolving, filtering, washing and
10h is dried in 32 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
12.55wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 1880g/mol, and fusing point is 83 DEG C, starting thermal decomposition temperature
Spend is 379 DEG C.
Embodiment 6
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the nitrogenous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in nitrogen protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 400rpm, and the temperature of fusion esterification reaction is 190
DEG C, the reaction time is 3h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle nitrogenous dicarboxylic acids of side base is：
2) by 2- carboxyethyl phenyl phosphinic acids and 1,4- butanediols with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides,
2- carboxyethyl phenyl phosphinic acids are 1 with the mol ratio of 4- toluene sulfonic acides:0.01, under conditions of nitrogen protection and mechanical agitation
Melt condensation reaction is carried out, churned mechanically mixing speed is 400rpm, and the temperature of melt condensation reaction is 190 DEG C, during reaction
Between be 2h, obtain end group be hydroxyl DADA；
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, argon gas is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 400rpm, fusion esterification reaction time be 4h, collect product, it is size-reduced, dissolving, filtering, washing and
11h is dried in 34 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
11.85wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 1992g/mol, and fusing point is 87 DEG C, starting thermal decomposition temperature
Spend is 378 DEG C.
Embodiment 7
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the nitrogenous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in argon gas protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 410rpm, and the temperature of fusion esterification reaction is 191
DEG C, the reaction time is 4h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle nitrogenous dicarboxylic acids of side base is：
2) by [(the own ring -6- bases of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha) methyl] succinic acid and ethylene glycol with
1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, [(the own ring -6- bases of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phosphas)
Methyl] mol ratio of succinic acid and 4- toluene sulfonic acides is 1:0.01, melted under conditions of argon gas protection and mechanical agitation
Melt condensation reaction, churned mechanically mixing speed is 410rpm, and the temperature of melt condensation reaction is 191 DEG C, and the reaction time is 3h,
Obtain the DADA that end group is hydroxyl；
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, argon gas is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 410rpm, fusion esterification reaction time be 4h, collect product, it is size-reduced, dissolving, filtering, washing and
12h is dried in 35 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
10.05wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 2348g/mol, and fusing point is 92 DEG C, starting thermal decomposition temperature
Spend is 360 DEG C.
Embodiment 8
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the nitrogenous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in nitrogen protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 425rpm, and the temperature of fusion esterification reaction is 193
DEG C, the reaction time is 4h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle nitrogenous dicarboxylic acids of side base is：
2) by [(the own ring -6- bases of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha) methyl] succinic acid and propane diols with
1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, [(the own ring -6- bases of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phosphas)
Methyl] mol ratio of succinic acid and 4- toluene sulfonic acides is 1:0.01, melted under conditions of nitrogen protection and mechanical agitation
Melt condensation reaction, churned mechanically mixing speed is 425rpm, and the temperature of melt condensation reaction is 193 DEG C, and the reaction time is 3h,
Obtain the DADA that end group is hydroxyl；
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, nitrogen is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 425rpm, fusion esterification reaction time be 3h, collect product, it is size-reduced, dissolving, filtering, washing and
14h is dried in 38 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
9.59wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 2460g/mol, and fusing point is 97 DEG C, initial heat decomposition temperature
It is 351 DEG C.
Embodiment 9
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the phosphorous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in nitrogen protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 444rpm, and the temperature of fusion esterification reaction is 195
DEG C, the reaction time is 3h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle phosphorous dicarboxylic acids of side base is：
2) by organic nitrogen-containing binary acid and 1,4- butanediols with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, organic
Nitrogenous binary acid is 1 with the mol ratio of 4- toluene sulfonic acides:0.01, melted under conditions of argon gas protection and mechanical agitation
Condensation reaction, churned mechanically mixing speed is 444rpm, and the temperature of melt condensation reaction is 195 DEG C, and the reaction time is 3h, is obtained
It is the DADA of hydroxyl to end group, wherein organic nitrogen-containing binary acid structural formula is：
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, argon gas is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 444rpm, fusion esterification reaction time be 3h, collect product, it is size-reduced, dissolving, filtering, washing and
15h is dried in 39 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
9.18wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 2572g/mol, and fusing point is 100 DEG C, starting thermal decomposition temperature
Spend is 348 DEG C.
Embodiment 10
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the phosphorous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in argon gas protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 458rpm, and the temperature of fusion esterification reaction is 196
DEG C, the reaction time is 3h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle phosphorous dicarboxylic acids of side base is：
2) by organic nitrogen-containing binary acid and ethylene glycol with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, organic nitrogen-containing
Binary acid is 1 with the mol ratio of 4- toluene sulfonic acides:0.01, carry out melt condensation under conditions of argon gas protection and mechanical agitation
Reaction, churned mechanically mixing speed is 458rpm, and the temperature of melt condensation reaction is 196 DEG C, and the reaction time is 3h, is held
Base is the DADA of hydroxyl, and wherein organic nitrogen-containing binary acid structural formula is：
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, argon gas is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 458rpm, fusion esterification reaction time be 2h, collect product, it is size-reduced, dissolving, filtering, washing and
15h is dried in 40 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
9.22wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 2560g/mol, and fusing point is 108 DEG C, starting thermal decomposition temperature
Spend is 350 DEG C.
Embodiment 11
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the phosphorous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in nitrogen protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 469rpm, and the temperature of fusion esterification reaction is 197
DEG C, the reaction time is 2h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle phosphorous dicarboxylic acids of side base is：
2) by organic nitrogen-containing binary acid and propane diols with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, organic nitrogen-containing
Binary acid is 1 with the mol ratio of 4- toluene sulfonic acides:0.01, carry out melt condensation under conditions of nitrogen protection and mechanical agitation
Reaction, churned mechanically mixing speed is 469rpm, and the temperature of melt condensation reaction is 197 DEG C, and the reaction time is 3h, is held
Base is the DADA of hydroxyl, and wherein organic nitrogen-containing binary acid structural formula is：
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, nitrogen is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 469rpm, fusion esterification reaction time be 2h, collect product, it is size-reduced, dissolving, filtering, washing and
16h is dried in 44 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
8.83wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 2672g/mol, and fusing point is 105 DEG C, starting thermal decomposition temperature
Spend is 345 DEG C.
Embodiment 12
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the phosphorous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in nitrogen protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 500rpm, and the temperature of fusion esterification reaction is 198
DEG C, the reaction time is 2h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle phosphorous dicarboxylic acids of side base is：
2) by organic nitrogen-containing binary acid and 1,4- butanediols with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, organic
Nitrogenous binary acid is 1 with the mol ratio of 4- toluene sulfonic acides:0.01, melted under conditions of argon gas protection and mechanical agitation
Condensation reaction, churned mechanically mixing speed is 500rpm, and the temperature of melt condensation reaction is 198 DEG C, and the reaction time is 1h, is obtained
It is the DADA of hydroxyl to end group, wherein organic nitrogen-containing binary acid structural formula is：
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, argon gas is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 500rpm, fusion esterification reaction time be 2h, collect product, it is size-reduced, dissolving, filtering, washing and
18h is dried in 44 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
8.48wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 2784g/mol, and fusing point is 111 DEG C, starting thermal decomposition temperature
Spend is 340 DEG C.
Embodiment 13
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the phosphorous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in argon gas protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 500rpm, and the temperature of fusion esterification reaction is 200
DEG C, the reaction time is 2h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle phosphorous dicarboxylic acids of side base is：
2) by organic nitrogen-containing binary acid and ethylene glycol with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, organic nitrogen-containing
Binary acid is 1 with the mol ratio of 4- toluene sulfonic acides:0.01, carry out melt condensation under conditions of argon gas protection and mechanical agitation
Reaction, churned mechanically mixing speed is 500rpm, and the temperature of melt condensation reaction is 200 DEG C, and the reaction time is 1h, is held
Base is the DADA of hydroxyl, and wherein organic nitrogen-containing binary acid structural formula is：
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, argon gas is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 500rpm, fusion esterification reaction time be 4h, collect product, it is size-reduced, dissolving, filtering, washing and
18h is dried in 50 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
9.22wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 2560g/mol, and fusing point is 125 DEG C, starting thermal decomposition temperature
Spend is 352 DEG C.
Embodiment 14
A kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group, step is as follows：
1) by the phosphorous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in nitrogen protection and mechanical agitation
Under conditions of carry out fusion esterification reaction, churned mechanically mixing speed is 500rpm, and the temperature of fusion esterification reaction is 200
DEG C, the reaction time is 4h, and reaction collects product after terminating, through dissolving, filtering and being dried to obtain the DAPER that end group is carboxyl, its
The structural formula of the middle phosphorous dicarboxylic acids of side base is：
2) by organic nitrogen-containing binary acid and propane diols with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, organic nitrogen-containing
Binary acid is 1 with the mol ratio of 4- toluene sulfonic acides:0.01, carry out melt condensation under conditions of nitrogen protection and mechanical agitation
Reaction, churned mechanically mixing speed is 500rpm, and the temperature of melt condensation reaction is 200 DEG C, and the reaction time is 1h, is held
Base is the DADA of hydroxyl, and wherein organic nitrogen-containing binary acid structural formula is：
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:
4, the temperature-resistant of system is kept, nitrogen is continually fed into, fusion esterification reaction, mechanical agitation are carried out under conditions of mechanical agitation
Mixing speed be 500rpm, fusion esterification reaction time be 4h, collect product, it is size-reduced, dissolving, filtering, washing and
18h is dried in 50 DEG C of vacuum drying oven and obtains the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
The molecular structural formula of the organic containing phosphorus-nitrogen carboxylate of final obtained terminal hydroxy group is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group, segment
In-CH2- be connected 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.
The total content of P elements and nitrogen is in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group for finally giving
8.83wt%, the molecular weight of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is 2672g/mol, and fusing point is 125 DEG C, starting thermal decomposition temperature
Spend is 346 DEG C.
Embodiment 15
A kind of fire-retardant polyester fibre FDY, preparation process is as follows：
(1) melt blending, by the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group obtained in dried embodiment 1 and PET cut into slices into
Row is mixed to get premix, and the wherein organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group and the mass ratio of PET sections is 3:97, by premix
Section is obtained flame retardant polyester section after melt blending under the conditions of 255 DEG C in the double screw extruder；
(2) melt spinning, the section of dried flame retardant polyester is through measuring, extruding, cool down, oil, stretch, thermal finalization and volume
Around prepared fire-retardant polyester fibre FDY, the technological parameter of melt spinning is：
Extrusion temperature：285℃；
Chilling temperature：20℃；
Network pressure：0.20MPa；
One roller speed：2200m/min；
One roll temperature：75℃；
Two roller speeds：3600m/min；
Two roll temperatures：115℃；
Winding speed：4000m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre FDY is 35%, and filament number is 3.0dtex, fracture
Intensity is 3.8cN/dtex, and elongation at break is 30%.
Embodiment 16
A kind of fire-retardant polyester fibre FDY, preparation process is as follows：
(1) melt blending, by the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group obtained in dried embodiment 2 and PET cut into slices into
Row is mixed to get premix, and the wherein organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group and the mass ratio of PET sections is 5:95, by premix
Section is obtained flame retardant polyester section after melt blending under the conditions of 257 DEG C in the double screw extruder；
(2) melt spinning, the section of dried flame retardant polyester is through measuring, extruding, cool down, oil, stretch, thermal finalization and volume
Around prepared fire-retardant polyester fibre FDY, the technological parameter of melt spinning is：
Extrusion temperature：288℃；
Chilling temperature：21℃；
Network pressure：0.22MPa；
One roller speed：2280m/min；
One roll temperature：78℃；
Two roller speeds：3660m/min；
Two roll temperatures：119℃；
Winding speed：4120m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre FDY is 35.5%, and filament number is 3.4dtex, is broken
Resistance to spalling is 3.85cN/dtex, and elongation at break is 31%.
Embodiment 17
A kind of fire-retardant polyester fibre FDY, preparation process is as follows：
(1) melt blending, by the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group obtained in dried embodiment 3 and PET cut into slices into
Row is mixed to get premix, and the wherein organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group and the mass ratio of PET sections is 7:93, by premix
Section is obtained flame retardant polyester section after melt blending under the conditions of 259 DEG C in the double screw extruder；
(2) melt spinning, the section of dried flame retardant polyester is through measuring, extruding, cool down, oil, stretch, thermal finalization and volume
Around prepared fire-retardant polyester fibre FDY, the technological parameter of melt spinning is：
Extrusion temperature：291℃；
Chilling temperature：22℃；
Network pressure：0.24MPa；
One roller speed：2360m/min；
One roll temperature：81℃；
Two roller speeds：3720m/min；
Two roll temperatures：123℃；
Winding speed：4240m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre FDY is 36.2%, and filament number is 3.8dtex, is broken
Resistance to spalling is 3.88cN/dtex, and elongation at break is 32%.
Embodiment 18
A kind of fire-retardant polyester fibre FDY, preparation process is as follows：
(1) melt blending, by the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group obtained in dried embodiment 4 and PET cut into slices into
Row is mixed to get premix, and the wherein organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group and the mass ratio of PET sections is 8:92, by premix
Section is obtained flame retardant polyester section after melt blending under the conditions of 261 DEG C in the double screw extruder；
(2) melt spinning, the section of dried flame retardant polyester is through measuring, extruding, cool down, oil, stretch, thermal finalization and volume
Around prepared fire-retardant polyester fibre FDY, the technological parameter of melt spinning is：
Extrusion temperature：294℃；
Chilling temperature：23℃；
Network pressure：0.26MPa；
One roller speed：2440m/min；
One roll temperature：84℃；
Two roller speeds：3780m/min；
Two roll temperatures：127℃；
Winding speed：4360m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre FDY is 37.7%, and filament number is 4.2dtex, is broken
Resistance to spalling is 4.0cN/dtex, and elongation at break is 33%.
Embodiment 19
A kind of fire-retardant polyester fibre FDY, preparation process is as follows：
(1) melt blending, by the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group obtained in dried embodiment 5 and PET cut into slices into
Row is mixed to get premix, and the wherein organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group and the mass ratio of PET sections is 9:91, by premix
Section is obtained flame retardant polyester section after melt blending under the conditions of 263 DEG C in the double screw extruder；
(2) melt spinning, the section of dried flame retardant polyester is through measuring, extruding, cool down, oil, stretch, thermal finalization and volume
Around prepared fire-retardant polyester fibre FDY, the technological parameter of melt spinning is：
Extrusion temperature：297℃；
Chilling temperature：24℃；
Network pressure：0.28MPa；
One roller speed：2520m/min；
One roll temperature：87℃；
Two roller speeds：3840m/min；
Two roll temperatures：131℃；
Winding speed：4480m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre FDY is 38.6%, and filament number is 4.6dtex, is broken
Resistance to spalling is 4.1cN/dtex, and elongation at break is 34%.
Embodiment 20
A kind of fire-retardant polyester fibre FDY, preparation process is as follows：
(1) melt blending, by the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group obtained in dried embodiment 6 and PET cut into slices into
Row is mixed to get premix, and the wherein organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group and the mass ratio of PET sections is 10:90, by premix
Section is obtained flame retardant polyester section after melt blending under the conditions of 265 DEG C in the double screw extruder；
(2) melt spinning, the section of dried flame retardant polyester is through measuring, extruding, cool down, oil, stretch, thermal finalization and volume
Around prepared fire-retardant polyester fibre FDY, the technological parameter of melt spinning is：
Extrusion temperature：300℃；
Chilling temperature：25℃；
Network pressure：0.30MPa；
One roller speed：2600m/min；
One roll temperature：90℃；
Two roller speeds：3900m/min；
Two roll temperatures：135℃；
Winding speed：4600m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre FDY is 39.5%, and filament number is 5.0dtex, is broken
Resistance to spalling is 4.2cN/dtex, and elongation at break is 36%.
Claims (10)
1. the preparation method of the organic containing phosphorus-nitrogen carboxylate of a kind of terminal hydroxy group, it is characterized in that, the organic containing phosphorus-nitrogen ester of terminal hydroxy group
The preparation method of compound is the melt condensation method based on reactant polyfunctional group reactivity difference, and the reactivity difference is
Referring to that the polyfunctional group in reactant is influenceed by steric hindrance has different reactivities, and polyfunctional group is according to reactivity
There is condensation reaction in order from high to low, step is as follows：
1) by side base dicarboxylic acids containing functional element and pentaerythrite with 4:1 mixed in molar ratio, in inert gas shielding and machine
Fusion esterification reaction is carried out under conditions of tool stirring, product is collected, it is post-treated to obtain the DAPER that end group is carboxyl；The side
Functional element is phosphorus or nitrogen, two carboxylic acid groups of the side base containing functional element dicarboxylic acids in base dicarboxylic acids containing functional element
Reactivity it is different, structural formula of the side base containing functional element dicarboxylic acids is one of following：
2) by organic binary acid containing functional element and dihydroxylic alcohols with 1:2 mixed in molar ratio, adds catalyst, is protected in inert gas
Melt condensation reaction is carried out under conditions of shield and mechanical agitation, the DADA that end group is hydroxyl is obtained；It is described organic containing functional element
Functional element in binary acid is phosphorus or nitrogen, the functional element in the functional element and the side base dicarboxylic acids containing functional element
Difference, the reactivity of two acidic-groups in organic binary acid containing functional element is different, described two acidic-groups
It is two carboxylic acid groups or phosphate and carboxylic acid group；
3) by step 1) in the DAPER that obtains be added to step 2) in system in, the mol ratio of DAPER and DADA is 1:4, protect
The temperature-resistant of system is held, inert gas is continually fed into, fusion esterification reaction is carried out under conditions of mechanical agitation, collected and produce
Thing, it is post-treated to obtain the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group.
2. a kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group according to claim 1, it is characterised in that step
It is rapid 1) in, the inert gas be nitrogen or argon gas, the churned mechanically mixing speed be 300~500rpm；The melting
The temperature of esterification is 180~200 DEG C, and the reaction time is 1~4h；The post processing includes dissolving, filtering and dries.
3. a kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group according to claim 1, it is characterised in that institute
Organic binary acid containing functional element is stated for phenyl-phosphonic acid, methylphosphonic acid, 2- carboxyethyl phenyl phosphinic acids, [(6- oxo -6H- hexichol
And the own ring -6- bases of [c, e] [1,2] oxygen phospha) methyl] one of succinic acid or the following compound of structural formula：
The dihydroxylic alcohols is ethylene glycol, propane diols or 1,4- butanediols.
4. a kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group according to claim 1, it is characterised in that step
It is rapid 2) in, the catalyst is 4- toluene sulfonic acides, and the mol ratio of organic binary acid containing functional element and catalyst is 1:
0.01, the inert gas is nitrogen or argon gas, and the churned mechanically mixing speed is 300~500rpm, the melting contracting
The temperature for closing reaction is 180~200 DEG C, and the reaction time is 1~3h.
5. a kind of preparation method of the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group according to claim 1, it is characterised in that step
It is rapid 3) in, the inert gas be nitrogen or argon gas, the churned mechanically mixing speed be 300~500rpm, the melting
The time of esterification be 1~4h, the post processing include crush, dissolve, being filtered, washed and dried, the drying refer to
6~18h of vacuum drying in 25~50 DEG C of vacuum drying oven.
6. using a kind of organic containing phosphorus-nitrogen esterification of terminal hydroxy group obtained in the preparation method as described in any one of Claims 1 to 5
Thing, it is characterized in that：The organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group is solid-state carboxylate, the organic containing phosphorus-nitrogen esterification of terminal hydroxy group
The molecular structural formula of thing is as follows：
In formula,The segment between the quaternary carbon C and R of the organic containing phosphorus-nitrogen carboxylate molecular center of terminal hydroxy group is represented, in segment-
CH2- be connected with the quaternary carbon C of carboxylate molecular center, concrete structure formula is following one kind：
The R is that end group is the long-chain containing functional element of hydroxyl, wherein, functional element is phosphorus or nitrogen；
The total content of P elements and nitrogen is 8.48~15.53wt% in the organic containing phosphorus-nitrogen carboxylate molecule of terminal hydroxy group.
7. the organic containing phosphorus-nitrogen carboxylate of a kind of terminal hydroxy group according to claim 6, it is characterised in that the end group is hydroxyl
The long-chain containing functional element of base is one of following structure：
Wherein, n=2,3,4.
8. the organic containing phosphorus-nitrogen carboxylate of a kind of terminal hydroxy group according to claim 6, it is characterised in that the terminal hydroxy group has
The molecular weight of machine containing phosphorus-nitrogen carboxylate is 1520~2784g/mol, and fusing point is 65~125 DEG C, and initial heat decomposition temperature is 340
~420 DEG C.
9. one kind is fire-retardant polyester fibre FDY as obtained in terminal hydroxy group as claimed in claim 6 organic containing phosphorus-nitrogen carboxylate,
It is characterized in that, the preparation process of fire-retardant polyester fibre FDY is as follows：
(1) melt blending, the organic containing phosphorus-nitrogen carboxylate of dried terminal hydroxy group and PET sections are carried out being mixed to get premix,
Flame retardant polyester section is obtained by being cut into slices after premix melt blending；
(2) melt spinning, dried flame retardant polyester section is through measuring, extruding, cool down, oil, stretch, thermal finalization and winding are made
Obtain fire-retardant polyester fibre FDY.
10. fire-retardant polyester fibre FDY according to claim 9, it is characterised in that the melt blending is in twin-screw
Carried out in extruder, the organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group and the mass ratio of PET sections are 3~10 during the melt blending:90
~97, the temperature of the melt blending is 255~265 DEG C；
The technological parameter of the melt spinning is：
Extrusion temperature：285~300 DEG C；
Chilling temperature：20~25 DEG C；
Network pressure：0.20~0.30MPa；
One roller speed：2200~2600m/min；
One roll temperature：75~90 DEG C；
Two roller speeds：3600~3900m/min；
Two roll temperatures：115~135 DEG C；
Winding speed：4000~4600m/min；
Limited oxygen index >=35% of described fire-retardant polyester fibre FDY, filament number be 3.0~5.0dtex, fracture strength >=
3.8cN/dtex, elongation at break is 33.0 ± 3.0%.
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Inventor after: Shen Li Inventor after: Sun Bin Inventor after: Xiang Hengxue Inventor after: Zhu Meifang Inventor after: Zhou Zhe Inventor after: Ji Huquan Inventor before: Du Jun Inventor before: Sun Bin Inventor before: Xiang Hengxue Inventor before: Zhu Meifang Inventor before: Zhou Zhe Inventor before: Teng Wei |