CN106810681A - A kind of terminal hydroxy group organic phosphorus esters compound and preparation method thereof and by its obtained flame retardant polyester fabric - Google Patents
A kind of terminal hydroxy group organic phosphorus esters compound and preparation method thereof and by its obtained flame retardant polyester fabric Download PDFInfo
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- CN106810681A CN106810681A CN201710032594.8A CN201710032594A CN106810681A CN 106810681 A CN106810681 A CN 106810681A CN 201710032594 A CN201710032594 A CN 201710032594A CN 106810681 A CN106810681 A CN 106810681A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
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Abstract
The present invention relates to a kind of terminal hydroxy group organic phosphorus esters compound and preparation method thereof and by its obtained flame retardant polyester fabric, the DAPER that end group is carboxyl is obtained by the phosphorous dicarboxylic acids of side base and the reaction of pentaerythrite first, then the DADA that end group is hydroxyl is obtained by organic phosphorous binary acid 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, the end group of molecule is hydroxyl, the internal P elements containing 7.8~11.74wt%, have the advantages that heat endurance is high, widely used, overcome the storage of traditional liquid type carboxylate and cause the shortcomings of purposes is single, preparation process pollutes environment using difficult, simple structure.Flame retardant polyester fabric is prepared using final products as fire retardant, the fire resistance of flame retardant polyester fabric is preferable, limited oxygen index >=32% of flame retardant polyester fabric.
Description
Technical field
The invention belongs to flame retardant area, it is related to a kind of terminal hydroxy group organic phosphorus esters compound and preparation method thereof and by its system
Flame retardant polyester fabric, more particularly to a kind of solid-state terminal hydroxy group organic phosphorus esters compound and its anti-based on reactant polyfunctional group
Answer the melt condensation preparation method of activity 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
Son amount solid type terminal hydroxy group organic phosphorus esters compound higher.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, the preparation method of the terminal hydroxy group organic phosphorus esters compound
It is the melt condensation method based on reactant polyfunctional group reactivity difference, the reactivity difference refers to many in reactant
Functional group is influenceed have different reactivities, order of the polyfunctional group according to reactivity from high to low by steric hindrance
Generation condensation reaction, step is as follows：
1) by the phosphorous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in inert gas shielding and machinery
Fusion esterification reaction is carried out under conditions of stirring, product is collected, it is post-treated to obtain the DAPER that end group is carboxyl；The side base
The reactivity of two carboxylic acid groups of phosphorous dicarboxylic acids is different, and the structural formula of the phosphorous dicarboxylic acids of side base is：
2) by organic phosphorous binary acid and dihydroxylic alcohols with 1:2 mixed in molar ratio, adds catalyst, in inert gas shielding
With melt condensation reaction is carried out under conditions of mechanical agitation, obtain end group be hydroxyl DADA；In organic phosphorous binary acid
Two reactivities of acidic-group are different, and described two acidic-groups are 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 terminal hydroxy group organic phosphorus esters compound.
As preferred technical scheme：
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound as described above, step 1) in, the inert gas is
Nitrogen or argon gas, the churned mechanically mixing speed are 300~500rpm；The temperature of fusion esterification reaction for 180~
200 DEG C, the reaction time is 1~4h；The post processing includes dissolving, filtering and dries.
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound as described above, organic phosphorous binary acid is phenyl
Phosphonic acids, methylphosphonic acid, 2- carboxyethyl phenyl phosphinic acids or the [(own ring -6- of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phosphas
Base) methyl] succinic acid, the dihydroxylic alcohols is ethylene glycol, propane diols or BDO.
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound as described above, step 2) in, the catalyst is 4-
Toluene sulfonic acide, organic phosphorous binary acid 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, and the temperature of the melt condensation reaction is 180~200 DEG C, instead
It is 1~3h between seasonable.
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound as described above, step 3) in, the inert gas is
Nitrogen or argon gas, the churned mechanically mixing speed are 300~500rpm, and the time of the fusion esterification reaction is 1~4h,
The post processing includes crushing, dissolves, is filtered, washed and dried.
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound as described above, the drying refers at 25~50 DEG C
6~18h of vacuum drying in vacuum drying oven.
Present invention also offers a kind of terminal hydroxy group organic phosphorus esters compound, the terminal hydroxy group organic phosphorus esters compound is solid-state
Carboxylate, the molecular structural formula of the terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center 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 phosphorous long-chain of hydroxyl；
The total content of P elements is 7.8~11.74wt% in the terminal hydroxy group organic phosphorus esters compound molecule.
As preferred technical scheme：
A kind of terminal hydroxy group organic phosphorus esters compound as described above, the end group is following structure for the phosphorous long-chain of hydroxyl
One of：
Wherein, n=2,3,4.
A kind of terminal hydroxy group organic phosphorus esters compound as described above, the molecular weight of the terminal hydroxy group organic phosphorus esters compound is
2112~3180g/mol, fusing point is 65~125 DEG C, and initial heat decomposition temperature is 340~420 DEG C.
Present invention also offers one kind as obtained in terminal hydroxy group organic phosphorus esters compound flame retardant polyester fabric, flame-resistant terylene knits
Thing is the fabric that two-sided forging line middle wefts structure is formed by warp thread and weft yarns, and wherein warp thread is non-flame resistant polyester filament,
Weft yarn is the fire-retardant polyester filament yarn of 5000~7000ppm of phosphorus content, and warp count is 80~165/cm, weft count in fabric
It is 20~45/cm, fire retardant is terminal hydroxy group organic phosphorus esters compound in fire-retardant polyester filament yarn.
Flame retardant polyester fabric as described above, the specification of the warp thread is 72D/36f-72f, and the specification of weft yarn is 135D/
48f-96f；Limited oxygen index >=32% of the flame retardant polyester fabric.
Carboxylate prepared by the present invention is, based on reactant polyfunctional group reactivity difference, to be obtained using melt condensation method
Solid-state terminal hydroxy group organic phosphorus esters compound, course of reaction depends on the multi-functional activity difference of reactant.The first step
The raw material used in course of reaction is the phosphorous dicarboxylic acids of side base, and two carboxyl-COOH are straight in the phosphorous dicarboxylic acids molecule of side base
Connect or by methylene-CH2- be connected with same tertiary carbon, because side base phosphorus-containing groups structure produces steric hindrance to imitate compared with conference
Should, make to pass through methylene-CH in the phosphorous dicarboxylic acids molecule of side base2The reactivity of-carboxyl-the COOH being connected with tertiary carbon is higher than
Carboxyl-the COOH being directly connected with tertiary carbon, in esterification reaction process, connects methylene-CH2- carboxyl-COOH can be prior to
There is esterification in hydroxyl-OH in pentaerythrite, form ester bond, and rubbing due to the phosphorous dicarboxylic acids of side base and pentaerythrite
You are than being 4:1, the two happens is that reactivity-COOH higher and season in end capping reaction, therefore the phosphorous dicarboxylic acids of side base
- OH reactions in penta tetrol stop after terminating, and the end group of the terminal hydroxy group organic phosphorus esters compound of generation is former side base phosphorous two
Relatively low carboxyl-the COOH of reactivity in first carboxylic acid molecules, the carboxyl-COOH participate in follow-up anti-as reaction active groups
Ying Zhong.
In second step course of reaction, organic phosphorous binary acid is also due to space steric effect Liang Ge functional groups (acidic groups
Group) reactivity have differences, when organic phosphorous binary acid and dihydroxylic alcohols mol ratio be 1:When 2, reactivity is higher
There is condensation reaction in functional group's (acidic-group), then the relatively low functional group of reactivity with the hydroxyl-OH in dihydroxylic alcohols first
(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 terminal hydroxy group organic phosphorus esters compound.
Beneficial effect：
1) the obtained carboxylate of the present invention is solid type terminal hydroxy group organic phosphorus esters compound, overcomes the esterification of traditional liquid type
The addition existed when thing is used as additive and the difficult shortcoming of storage；
2) the obtained organic phosphorus esters compound end group of the present invention contains abundant hydroxyl, and its molecular structure can be set
Meter, as the reaction monomers of further reaction, prepares multi-functional compounds；
3) the obtained terminal hydroxy group organic phosphorus esters compound molecular weight of the present invention is (2112~3180g/mol) higher, and is star
Type structure, when being used as additive, it is possible to increase the compatibility with polymer, overcomes small-molecular-weight additive easily to migrate, resistance to
The problem of long property difference；
4) when the obtained terminal hydroxy group organic phosphorus esters compound of the present invention is used as functional additive, have with polymeric matrix
There is good compatibility, because phosphorus element content is (7.8~11.74wt%) higher, in the feelings of addition less (being less than 5wt%)
Preferable modified effect can be reached under condition；
5) method for preparing terminal hydroxy group organic phosphorus esters compound of the invention is simple, belongs to melt condensation, without using a large amount of
Solvent, environmental protection will not be conducive to environmental effects, 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 terminal hydroxy group organic phosphorus esters compound, 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 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 phosphorous 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 argon gas 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 terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 10.62wt%, terminal hydroxy group in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving
The molecular weight of organic phosphorus esters compound is 2336g/mol, and fusing point is 65 DEG C, and initial heat decomposition temperature is 400 DEG C.
Embodiment 2
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, 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 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 phosphorous 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 argon gas 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 terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 10.13wt%, terminal hydroxy group in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving
The molecular weight of organic phosphorus esters compound is 2448g/mol, and fusing point is 68 DEG C, and initial heat decomposition temperature is 395 DEG C.
Embodiment 3
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, 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 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 phosphorous dicarboxylic acids of side base is：
2) by phenyl-phosphonic acid and 1,4- butanediols with 1:2 mixed in molar ratio, add 4- toluene sulfonic acides, phenyl-phosphonic 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, nitrogen 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 terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 9.69wt% in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving, and terminal hydroxy group has
The molecular weight of the phosphorous carboxylate of machine is 2560g/mol, and fusing point is 74 DEG C, and initial heat decomposition temperature is 383 DEG C.
Embodiment 4
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, 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 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 phosphorous 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 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 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 terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 11.74wt%, terminal hydroxy group in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving
The molecular weight of organic phosphorus esters compound is 2112g/mol, and fusing point is 79 DEG C, and initial heat decomposition temperature is 420 DEG C.
Embodiment 5
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, 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 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 phosphorous dicarboxylic acids of side base is：
2) by methylphosphonic acid and propane diols 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 383rpm, and the temperature of melt condensation reaction is 188 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, 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 terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 11.15wt%, terminal hydroxy group in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving
The molecular weight of organic phosphorus esters compound is 2224g/mol, and fusing point is 88 DEG C, and initial heat decomposition temperature is 412 DEG C.
Embodiment 6
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, 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 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 phosphorous 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 400rpm, and the temperature of melt condensation reaction is 190 DEG C, and the reaction time is 2h, 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, nitrogen 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 3h, collect product, it is size-reduced, dissolving, filtering, washing and
11h is dried in 34 DEG C of vacuum drying oven and obtains terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 10.62wt%, terminal hydroxy group in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving
The molecular weight of organic phosphorus esters compound is 2336g/mol, and fusing point is 95 DEG C, and initial heat decomposition temperature is 399 DEG C.
Embodiment 7
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, 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 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 phosphorous dicarboxylic acids of side base is：
2) by 2- carboxyethyl phenyl phosphinic acids and ethylene glycol 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 argon gas protection and mechanical agitation
Melt condensation reacts, and churned mechanically mixing speed is 410rpm, and the temperature of melt condensation reaction is 191 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 410rpm, fusion esterification reaction time be 4h, collect product, it is size-reduced, dissolving, filtering, washing and
12h is dried in 38 DEG C of vacuum drying oven and obtains terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 10.39wt%, terminal hydroxy group in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving
The molecular weight of organic phosphorus esters compound is 2388g/mol, and fusing point is 98 DEG C, and initial heat decomposition temperature is 398 DEG C.
Embodiment 8
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, 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 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 phosphorous 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 argon gas protection and mechanical agitation
Melt condensation reacts, and churned mechanically mixing speed is 425rpm, and the temperature of melt condensation reaction is 193 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 425rpm, fusion esterification reaction time be 4h, collect product, it is size-reduced, dissolving, filtering, washing and
14h is dried in 39 DEG C of vacuum drying oven and obtains terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 9.92wt% in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving, and terminal hydroxy group has
The molecular weight of the phosphorous carboxylate of machine is 2500g/mol, and fusing point is 100 DEG C, and initial heat decomposition temperature is 381 DEG C.
Embodiment 9
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, 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 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 argon gas protection and mechanical agitation
Melt condensation reaction is carried out, churned mechanically mixing speed is 444rpm, and the temperature of melt condensation reaction is 195 DEG C, during reaction
Between be 3h, 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, nitrogen 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 40 DEG C of vacuum drying oven and obtains terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 9.49wt% in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving, and terminal hydroxy group has
The molecular weight of the phosphorous carboxylate of machine is 2612g/mol, and fusing point is 108 DEG C, and initial heat decomposition temperature is 378 DEG C.
Embodiment 10
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, 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 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 [(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 458rpm, and the temperature of melt condensation reaction is 196 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 458rpm, fusion esterification reaction time be 3h, collect product, it is size-reduced, dissolving, filtering, washing and
16h is dried in 44 DEG C of vacuum drying oven and obtains terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 8.08wt% in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving, and terminal hydroxy group has
The molecular weight of the phosphorous carboxylate of machine is 3068g/mol, and fusing point is 113 DEG C, and initial heat decomposition temperature is 355 DEG C.
Embodiment 11
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, 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 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 [(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 argon gas protection and mechanical agitation
Melt condensation reaction, churned mechanically mixing speed is 469rpm, and the temperature of melt condensation reaction is 198 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 469rpm, fusion esterification reaction time be 2h, collect product, it is size-reduced, dissolving, filtering, washing and
17h is dried in 48 DEG C of vacuum drying oven and obtains terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 7.94wt% in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving, and terminal hydroxy group has
The molecular weight of the phosphorous carboxylate of machine is 3124g/mol, and fusing point is 120 DEG C, and initial heat decomposition temperature is 348 DEG C.
Embodiment 12
A kind of preparation method of terminal hydroxy group organic phosphorus esters compound, 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 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 [(the own ring -6- bases of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha) methyl] succinic acid and 1,4- fourths two
Alcohol is with 1:2 mixed in molar ratio, adds 4- toluene sulfonic acides, [(the own ring of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phosphas -
6- yls) methyl] mol ratio of succinic acid and 4- toluene sulfonic acides is 1:0.01, enter under conditions of argon gas protection and mechanical agitation
Row melt condensation reacts, and churned mechanically mixing speed is 500rpm, and the temperature of melt condensation reaction is 200 DEG C, reaction time
It is 3h, 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 500rpm, fusion esterification reaction time be 2h, collect product, it is size-reduced, dissolving, filtering, washing and
18h is dried in 50 DEG C of vacuum drying oven and obtains terminal hydroxy group organic phosphorus esters compound.
The molecular structural formula of final obtained terminal hydroxy group organic phosphorus esters compound is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center is represented, in segment
- 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 is 7.8wt% in the terminal hydroxy group organic phosphorus esters compound molecule for finally giving, and terminal hydroxy group has
The molecular weight of the phosphorous carboxylate of machine is 3180g/mol, and fusing point is 125 DEG C, and initial heat decomposition temperature is 340 DEG C.
Embodiment 13
A kind of flame retardant polyester fabric, with non-flame resistant polyester filament as warp thread, the fire-retardant polyester filament yarn of phosphorus content 5000ppm is
Weft yarn, fire retardant is terminal hydroxy group organic phosphorus esters compound obtained in embodiment 1, warp thread and weft yarns shape in fire-retardant polyester filament yarn
Fabric into two-sided forging line middle wefts structure is flame retardant polyester fabric, wherein, warp count is 80/cm, weft yarn in fabric
Density is 20/cm, and the specification of warp thread is 72D/36f, and the specification of weft yarn is 135D/48f, final obtained flame retardant polyester fabric
Limited oxygen index be 32%.
Embodiment 14
A kind of flame retardant polyester fabric, with non-flame resistant polyester filament as warp thread, the fire-retardant polyester filament yarn of phosphorus content 5400ppm is
Weft yarn, fire retardant is terminal hydroxy group organic phosphorus esters compound obtained in embodiment 2, warp thread and weft yarns shape in fire-retardant polyester filament yarn
Fabric into two-sided forging line middle wefts structure is flame retardant polyester fabric, wherein, warp count is 97/cm, weft yarn in fabric
Density is 25/cm, and the specification of warp thread is 72D/43f, and the specification of weft yarn is 135D/57f, final obtained flame retardant polyester fabric
Limited oxygen index be 32.5%.
Embodiment 15
A kind of flame retardant polyester fabric, with non-flame resistant polyester filament as warp thread, the fire-retardant polyester filament yarn of phosphorus content 5800ppm is
Weft yarn, fire retardant is terminal hydroxy group organic phosphorus esters compound obtained in embodiment 3, warp thread and weft yarns shape in fire-retardant polyester filament yarn
Fabric into two-sided forging line middle wefts structure is flame retardant polyester fabric, wherein, warp count is 114/cm, weft yarn in fabric
Density is 30/cm, and the specification of warp thread is 72D/50f, and the specification of weft yarn is 135D/64f, final obtained flame retardant polyester fabric
Limited oxygen index be 33.1%.
Embodiment 16
A kind of flame retardant polyester fabric, with non-flame resistant polyester filament as warp thread, the fire-retardant polyester filament yarn of phosphorus content 6200ppm is
Weft yarn, fire retardant is terminal hydroxy group organic phosphorus esters compound obtained in embodiment 4, warp thread and weft yarns shape in fire-retardant polyester filament yarn
Fabric into two-sided forging line middle wefts structure is flame retardant polyester fabric, wherein, warp count is 131/cm, weft yarn in fabric
Density is 35/cm, and the specification of warp thread is 72D/58f, and the specification of weft yarn is 135D/73f, final obtained flame retardant polyester fabric
Limited oxygen index be 33.9%.
Embodiment 17
A kind of flame retardant polyester fabric, with non-flame resistant polyester filament as warp thread, the fire-retardant polyester filament yarn of phosphorus content 6600ppm is
Weft yarn, fire retardant is terminal hydroxy group organic phosphorus esters compound obtained in embodiment 5, warp thread and weft yarns shape in fire-retardant polyester filament yarn
Fabric into two-sided forging line middle wefts structure is flame retardant polyester fabric, wherein, warp count is 148/cm, weft yarn in fabric
Density is 40/cm, and the specification of warp thread is 72D/65f, and the specification of weft yarn is 135D/83f, final obtained flame retardant polyester fabric
Limited oxygen index be 34.3%.
Embodiment 18
A kind of flame retardant polyester fabric, with non-flame resistant polyester filament as warp thread, the fire-retardant polyester filament yarn of phosphorus content 7000ppm is
Weft yarn, fire retardant is terminal hydroxy group organic phosphorus esters compound obtained in embodiment 6, warp thread and weft yarns shape in fire-retardant polyester filament yarn
Fabric into two-sided forging line middle wefts structure is flame retardant polyester fabric, wherein, warp count is 165/cm, weft yarn in fabric
Density is 45/cm, and the specification of warp thread is 72D/72f, and the specification of weft yarn is 135D/96f, final obtained flame retardant polyester fabric
Limited oxygen index be 35.2%.
Claims (10)
1. a kind of preparation method of terminal hydroxy group organic phosphorus esters compound, it is characterized in that, the terminal hydroxy group organic phosphorus esters compound
Preparation method is the melt condensation method based on reactant polyfunctional group reactivity difference, and the reactivity difference refers to reaction
Polyfunctional group in thing is influenceed have different reactivities by steric hindrance, polyfunctional group according to reactivity by height to
There is condensation reaction in low order, step is as follows：
1) by the phosphorous dicarboxylic acids of side base and pentaerythrite with 4:1 mixed in molar ratio, in inert gas shielding and mechanical agitation
Under conditions of carry out fusion esterification reaction, collect product, it is post-treated to obtain the DAPER that end group is carboxyl；The side base is phosphorous
The reactivity of two carboxylic acid groups of dicarboxylic acids is different, and the structural formula of the phosphorous dicarboxylic acids of side base is：
2) by organic phosphorous binary acid and dihydroxylic alcohols with 1:2 mixed in molar ratio, adds catalyst, in inert gas shielding and machine
Melt condensation reaction is carried out under conditions of tool stirring, the DADA that end group is hydroxyl is obtained；Two in organic phosphorous binary acid
The reactivity of acidic-group is different, and described two acidic-groups are 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 terminal hydroxy group organic phosphorus esters compound.
2. the preparation method of a kind of terminal hydroxy group organic phosphorus esters compound according to claim 1, it is characterised in that step 1)
In, the inert gas is nitrogen or argon gas, and the churned mechanically mixing speed is 300~500rpm；The fusion esterification
The temperature of reaction is 180~200 DEG C, and the reaction time is 1~4h；The post processing includes dissolving, filtering and dries.
3. the preparation method of a kind of terminal hydroxy group organic phosphorus esters compound according to claim 1, it is characterised in that described to have
The phosphorous binary acid of machine is phenyl-phosphonic acid, methylphosphonic acid, 2- carboxyethyl phenyl phosphinic acids or [(6- oxo -6H- dibenzo [c, e]
Own ring -6- the bases of [1,2] oxygen phospha) methyl] succinic acid, the dihydroxylic alcohols is ethylene glycol, propane diols or BDO.
4. the preparation method of a kind of terminal hydroxy group organic phosphorus esters compound according to claim 1, it is characterised in that step 2)
In, the catalyst is 4- toluene sulfonic acides, and organic phosphorous binary acid is 1 with the mol ratio of catalyst:0.01, it is described lazy
Property gas be nitrogen or argon gas, the churned mechanically mixing speed is 300~500rpm, the temperature of melt condensation reaction
It it is 180~200 DEG C, the reaction time is 1~3h.
5. the preparation method of a kind of terminal hydroxy group organic phosphorus esters compound according to claim 1, it is characterised in that step 3)
In, the inert gas is nitrogen or argon gas, and the churned mechanically mixing speed is 300~500rpm, the fusion esterification
The time of reaction is 1~4h, and the post processing includes crushing, dissolving, being filtered, washed and dried, the drying refer to 25~
6~18h of vacuum drying in 50 DEG C of vacuum drying oven.
6. using a kind of terminal hydroxy group organic phosphorus esters compound obtained in the preparation method as described in any one of Claims 1 to 5, its
It is characterized in：The terminal hydroxy group organic phosphorus esters compound is solid-state carboxylate, the molecule knot of the terminal hydroxy group organic phosphorus esters compound
Structure formula is as follows：
In formula,The segment between the quaternary carbon C and R of terminal hydroxy group organic phosphorus esters compound molecular center 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 phosphorous long-chain of hydroxyl；
The total content of P elements is 7.8~11.74wt% in the terminal hydroxy group organic phosphorus esters compound molecule.
7. a kind of terminal hydroxy group organic phosphorus esters compound according to claim 6, it is characterised in that the end group is hydroxyl
Phosphorous long-chain is one of following structure：
Wherein, n=2,3,4.
8. a kind of terminal hydroxy group organic phosphorus esters compound according to claim 6, it is characterised in that the terminal hydroxy group is organic to be contained
The molecular weight of phosphide compound is 2112~3180g/mol, and fusing point is 65~125 DEG C, and initial heat decomposition temperature is 340~420 DEG C.
9. one kind flame retardant polyester fabric as obtained in terminal hydroxy group organic phosphorus esters compound as claimed in claim 6, it is characterized in that：
Flame retardant polyester fabric is the fabric that two-sided forging line middle wefts structure is formed by warp thread and weft yarns, and wherein warp thread is non-flame resistant
Polyester filament, weft yarn for 5000~7000ppm of phosphorus content fire-retardant polyester filament yarn, in fabric warp count be 80~165/
Cm, weft count is 20~45/cm, and fire retardant is terminal hydroxy group organic phosphorus esters compound in fire-retardant polyester filament yarn.
10. flame retardant polyester fabric according to claim 9, it is characterised in that the specification of the warp thread is 72D/36f-
72f, the specification of weft yarn is 135D/48f-96f；Limited oxygen index >=32% of the flame retardant polyester fabric.
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| CN109797448A (en) * | 2018-12-13 | 2019-05-24 | 上海东华镜月资产经营有限公司 | The cross carboxylate and preparation method thereof of the easily distributed loaded metal ion of water phase |
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