CN106835340A - A kind of organic phosphorous thioesters compound of end sulfydryl and preparation method thereof and obtained fire-retardant polyester fibre HOY by its - Google Patents
A kind of organic phosphorous thioesters compound of end sulfydryl and preparation method thereof and obtained fire-retardant polyester fibre HOY by its Download PDFInfo
- Publication number
- CN106835340A CN106835340A CN201710030664.6A CN201710030664A CN106835340A CN 106835340 A CN106835340 A CN 106835340A CN 201710030664 A CN201710030664 A CN 201710030664A CN 106835340 A CN106835340 A CN 106835340A
- Authority
- CN
- China
- Prior art keywords
- sulfydryl
- organic phosphorous
- phosphorous
- organic
- thioesters compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to organic phosphorous thioesters compound of a kind of end sulfydryl and preparation method thereof and obtained fire-retardant polyester fibre HOY by its, the DAPER that end group is carboxyl is obtained by the phosphorous dicarboxylic acids of side base and the reaction of pentaerythrite first, then one end is obtained for sulfydryl, the other end are the DADA of hydroxyl by organic monocarboxylic acid containing sulfydryl 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 sulfydryl, and internal P elements and element sulphur containing 12.4~13.13wt% have the advantages that heat endurance is high, widely used.Fire-retardant polyester fibre HOY is prepared by melt spinning method using final products as fire retardant, limited oxygen index >=34% of fire-retardant polyester fibre HOY, filament number is 0.3~2.0dtex, fracture strength >=3.0cN/dtex.
Description
Technical field
The invention belongs to flame retardant area, be related to organic phosphorous-thioesters compound of a kind of end sulfydryl and preparation method thereof and by
Its obtained fire-retardant polyester fibre HOY, more particularly to a kind of organic phosphorous-thioesters compound of solid-state end sulfydryl 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
Son amount sulfydryl organic phosphorous-thioesters compound in solid type end higher.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of preparation method of the organic phosphorous-thioesters compound of end sulfydryl, the system of the organic phosphorous-thioesters compound of end sulfydryl
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 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 monocarboxylic acid containing sulfydryl and dihydroxylic alcohols with 1:1 mixed in molar ratio, adds catalyst, in inert gas
Melt condensation reaction is carried out under conditions of protection and mechanical agitation, one end is obtained for sulfydryl, the other end are the DADA of hydroxyl；It is described
Sulfydryl is different with the reactivity of carboxylic acid group in organic monocarboxylic acid containing sulfydryl；
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 holding the organic phosphorous-thioesters compound of sulfydryl.
As preferred technical scheme：
A kind of preparation method of the organic phosphorous-thioesters compound of end sulfydryl 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 phosphorous-thioesters compound of end sulfydryl as described above, organic carboxylic of unitary containing sulfydryl
The structural formula of acid is as follows：
The dihydroxylic alcohols is ethylene glycol, propane diols or 1,4- butanediols.
A kind of preparation method of the organic phosphorous-thioesters compound of end sulfydryl as described above, step 2) in, the catalyst is
4- toluene sulfonic acides, organic monocarboxylic acid containing sulfydryl is 1 with the mol ratio of catalyst:0.01, the inert gas is nitrogen
Gas or argon gas, the churned mechanically mixing speed are 300~500rpm, and the temperature of the melt condensation reaction is 180~200
DEG C, the reaction time is 1~3h.
A kind of preparation method of the organic phosphorous-thioesters compound of end sulfydryl 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 phosphorous-thioesters compound of end sulfydryl 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 phosphorous-thioesters compound of end sulfydryl, the organic phosphorous-thioesters compound of end sulfydryl
It is solid-state carboxylate, the molecular structural formula of the organic phosphorous-thioesters compound of end sulfydryl is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic phosphorous-thioesters compound molecular center of end sulfydryl, segment
In-CH2- be connected with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows：
The R is that end group is the long-chain of sulfydryl；
In the organic phosphorous-thioesters compound molecule of end sulfydryl the total content of P elements and element sulphur be 12.4~
13.13wt%.
As preferred technical scheme：
A kind of organic phosphorous-thioesters compound of end sulfydryl as described above, the end group is following structure for the long-chain of sulfydryl：
Wherein, n=2,3,4.
A kind of organic phosphorous-thioesters compound of end sulfydryl as described above, the organic phosphorous-thioesters compound of end sulfydryl point
Son amount is 1920~2032g/mol, and fusing point is 65~125 DEG C, and initial heat decomposition temperature is 340~420 DEG C.
Present invention also offers one kind fire-retardant polyester fibre HOY as obtained in end sulfydryl organic phosphorous-thioesters compound, resistance
The preparation process that retardant polyester fiber is HOY is as follows：
(1) melt blending, the organic phosphorous-thioesters compound of dried end sulfydryl 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, dried flame retardant polyester section is obtained resistance through measuring, extruding, cool down, oil with high-speed winding
Retardant polyester fiber HOY.
Fire-retardant polyester fibre HOY as described above, the melt blending is being carried out in double screw extruder, described molten
Organic phosphorous-thioesters the compound of end sulfydryl 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：290~300 DEG C；
Chilling temperature：20~25 DEG C；
High-speed winding speed：5000~7000m/min；
Limited oxygen index >=34% of described fire-retardant polyester fibre HOY, filament number is 0.3~2.0dtex, and fracture is strong
Degree >=3.0cN/dtex, elongation at break is 50.0 ± 4.0%.
Carboxylate prepared by the present invention is, based on reactant polyfunctional group reactivity difference, to be obtained using melt condensation method
The organic phosphorous-thioesters compound of solid-state end sulfydryl, course of reaction depends on the multi-functional activity difference of reactant.First
The raw material used in step course of reaction is the phosphorous dicarboxylic acids of side base, two carboxyl-COOH in the phosphorous dicarboxylic acids molecule of side base
Directly or by methylene-CH2- be connected with same tertiary carbon, because side base phosphorus-containing groups structure produces steric hindrance compared with conference
Effect, makes 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 high
In the carboxyl-COOH being directly connected with tertiary carbon, in esterification reaction process, methylene-CH is connected2- carboxyl-COOH can be first
There is esterification in the hydroxyl-OH in pentaerythrite, form ester bond, and due to the phosphorous dicarboxylic acids of side base and pentaerythrite
Mol ratio is 4:1, the two happens is that in end capping reaction, therefore the phosphorous dicarboxylic acids of side base reactivity-COOH higher with
- OH reactions in pentaerythrite stop after terminating, and the end group of the organic phosphorous-thioesters compound of end sulfydryl of generation is that former side base contains
Relatively low carboxyl-the COOH of reactivity in phosphorus dicarboxylic acids molecule, the carboxyl-COOH are participated in subsequently as reaction active groups
Reaction in.
In second step course of reaction, organic monocarboxylic acid containing sulfydryl is also due to space steric effect Liang Ge functional groups (mercapto
Base and carboxylic acid group) reactivity have differences, when organic monocarboxylic acid containing sulfydryl and dihydroxylic alcohols mol ratio be 1:When 1, have
In machine monocarboxylic acid containing sulfydryl there is condensation reaction in reactivity carboxylic acid group higher with the hydroxyl-OH in dihydroxylic alcohols, generation
Carboxylate one end is hydroxyl-OH, and the other end is the relatively low sulfydryl of reactivity in original machine monocarboxylic acid containing sulfydryl molecule.
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 holding the organic phosphorous-thioesters compound of sulfydryl.
Beneficial effect：
1) the obtained carboxylate of the present invention is the organic phosphorous-thioesters compound of solid type end sulfydryl, overcomes traditional liquid type
The addition existed when carboxylate is used as additive and the difficult shortcoming of storage；
2) the obtained organic phosphorous-thioesters compound end group of the present invention contains abundant sulfydryl, and its molecular structure can be entered
Row design, as the reaction monomers of further reaction, prepares multi-functional compounds；
3) the obtained end organic phosphorous-thioesters compound molecular weight of sulfydryl of the present invention is (1920~2032g/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 end organic phosphorous-thioesters compound of sulfydryl of the present invention is used as functional additive, with polymer matrix
Body has good compatibility, less in addition because P elements and sulfur content are (12.4~13.13wt%) higher
Preferable modified effect can be reached in the case of (being less than 5wt%)；
5) the organic phosphorous-thioesters compound of the obtained end sulfydryl of the present invention not only containing P elements but also contained element sulphur, Neng Gouqi
To good synergy；
6) method of the present invention preparation organic phosphorous-thioesters compound of end sulfydryl 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 phosphorous-thioesters compound of end sulfydryl, 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 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 organic monocarboxylic acid containing sulfydryl and ethylene glycol with 1:1 mixed in molar ratio, adds 4- toluene sulfonic acides, organic
Monocarboxylic acid containing sulfydryl is 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 300rpm, and the temperature of melt condensation reaction is 180 DEG C, and the reaction time is
1h, obtains one end for sulfydryl, the other end are the DADA of hydroxyl, wherein organic monocarboxylic acid containing sulfydryl 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 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 to obtain holding the organic phosphorous-thioesters compound of sulfydryl.
The molecular structural formula of the final obtained end organic phosphorous-thioesters compound of sulfydryl is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic phosphorous-thioesters compound molecular center of end sulfydryl, 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 element sulphur is in the organic phosphorous-thioesters compound molecule of end sulfydryl for finally giving
13.13wt%, the molecular weight for holding the organic phosphorous-thioesters compound of sulfydryl is 1920g/mol, and fusing point is 65 DEG C, starting thermal decomposition temperature
Spend is 420 DEG C.
Embodiment 2
A kind of preparation method of the organic phosphorous-thioesters compound of end sulfydryl, 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 300rpm, and the temperature of fusion esterification reaction is 185
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 organic monocarboxylic acid containing sulfydryl and propane diols with 1:1 mixed in molar ratio, adds 4- toluene sulfonic acides, organic
Monocarboxylic acid containing sulfydryl is 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 300rpm, and the temperature of melt condensation reaction is 185 DEG C, and the reaction time is
1h, obtains one end for sulfydryl, the other end are the DADA of hydroxyl, wherein organic monocarboxylic acid containing sulfydryl 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 300rpm, fusion esterification reaction time be 1h, collect product, it is size-reduced, dissolving, filtering, washing and
8h is dried in 28 DEG C of vacuum drying oven to obtain holding the organic phosphorous-thioesters compound of sulfydryl.
The molecular structural formula of the final obtained end organic phosphorous-thioesters compound of sulfydryl is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic phosphorous-thioesters compound molecular center of end sulfydryl, 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 element sulphur is in the organic phosphorous-thioesters compound molecule of end sulfydryl for finally giving
12.75wt%, the molecular weight for holding the organic phosphorous-thioesters compound of sulfydryl is 1976g/mol, and fusing point is 80 DEG C, starting thermal decomposition temperature
Spend is 373 DEG C.
Embodiment 3
A kind of preparation method of the organic phosphorous-thioesters compound of end sulfydryl, 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 350rpm, and the temperature of fusion esterification reaction is 190
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 monocarboxylic acid containing sulfydryl and 1,4- butanediols with 1:1 mixed in molar ratio, adds 4- toluene sulfonic acides,
Organic monocarboxylic acid containing sulfydryl is 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 350rpm, and the temperature of melt condensation reaction is 190 DEG C, during reaction
Between be 2h, obtain one end for sulfydryl, the other end for hydroxyl DADA, wherein organic monocarboxylic acid containing sulfydryl 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 350rpm, fusion esterification reaction time be 2h, collect product, it is size-reduced, dissolving, filtering, washing and
10h is dried in 30 DEG C of vacuum drying oven to obtain holding the organic phosphorous-thioesters compound of sulfydryl.
The molecular structural formula of the final obtained end organic phosphorous-thioesters compound of sulfydryl is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic phosphorous-thioesters compound molecular center of end sulfydryl, 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 element sulphur is in the organic phosphorous-thioesters compound molecule of end sulfydryl for finally giving
12.4wt%, the molecular weight for holding the organic phosphorous-thioesters compound of sulfydryl is 2032g/mol, and fusing point is 95 DEG C, initial heat decomposition temperature
It is 340 DEG C.
Embodiment 4
A kind of preparation method of the organic phosphorous-thioesters compound of end sulfydryl, 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 400rpm, and the temperature of fusion esterification reaction is 194
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 monocarboxylic acid containing sulfydryl and ethylene glycol with 1:1 mixed in molar ratio, adds 4- toluene sulfonic acides, organic
Monocarboxylic acid containing sulfydryl is 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 400rpm, and the temperature of melt condensation reaction is 194 DEG C, and the reaction time is
2h, obtains one end for sulfydryl, the other end are the DADA of hydroxyl, wherein organic monocarboxylic acid containing sulfydryl 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 400rpm, fusion esterification reaction time be 3h, collect product, it is size-reduced, dissolving, filtering, washing and
12h is dried in 35 DEG C of vacuum drying oven to obtain holding the organic phosphorous-thioesters compound of sulfydryl.
The molecular structural formula of the final obtained end organic phosphorous-thioesters compound of sulfydryl is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic phosphorous-thioesters compound molecular center of end sulfydryl, 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 element sulphur is in the organic phosphorous-thioesters compound molecule of end sulfydryl for finally giving
13.13wt%, the molecular weight for holding the organic phosphorous-thioesters compound of sulfydryl is 1920g/mol, and fusing point is 110 DEG C, starting thermal decomposition temperature
Spend is 420 DEG C.
Embodiment 5
A kind of preparation method of the organic phosphorous-thioesters compound of end sulfydryl, 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 420rpm, and the temperature of fusion esterification reaction is 198
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 monocarboxylic acid containing sulfydryl and propane diols with 1:1 mixed in molar ratio, adds 4- toluene sulfonic acides, organic
Monocarboxylic acid containing sulfydryl is 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 420rpm, and the temperature of melt condensation reaction is 198 DEG C, and the reaction time is
3h, obtains one end for sulfydryl, the other end are the DADA of hydroxyl, wherein organic monocarboxylic acid containing sulfydryl 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 420rpm, 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 to obtain holding the organic phosphorous-thioesters compound of sulfydryl.
The molecular structural formula of the final obtained end organic phosphorous-thioesters compound of sulfydryl is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic phosphorous-thioesters compound molecular center of end sulfydryl, 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 element sulphur is in the organic phosphorous-thioesters compound molecule of end sulfydryl for finally giving
12.75wt%, the molecular weight for holding the organic phosphorous-thioesters compound of sulfydryl is 1976g/mol, and fusing point is 122 DEG C, starting thermal decomposition temperature
Spend is 381 DEG C.
Embodiment 6
A kind of preparation method of the organic phosphorous-thioesters compound of end sulfydryl, 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 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 monocarboxylic acid containing sulfydryl and 1,4- butanediols with 1:1 mixed in molar ratio, adds 4- toluene sulfonic acides,
Organic monocarboxylic acid containing sulfydryl is 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 500rpm, and the temperature of melt condensation reaction is 200 DEG C, during reaction
Between be 3h, obtain one end for sulfydryl, the other end for hydroxyl DADA, wherein organic monocarboxylic acid containing sulfydryl 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 to obtain holding the organic phosphorous-thioesters compound of sulfydryl.
The molecular structural formula of the final obtained end organic phosphorous-thioesters compound of sulfydryl is as follows：
In formula,Represent the segment between the quaternary carbon C and R of the organic phosphorous-thioesters compound molecular center of end sulfydryl, 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 element sulphur is in the organic phosphorous-thioesters compound molecule of end sulfydryl for finally giving
12.4wt%, the molecular weight for holding the organic phosphorous-thioesters compound of sulfydryl is 2032g/mol, and fusing point is 125 DEG C, starting thermal decomposition temperature
Spend is 340 DEG C.
Embodiment 7
A kind of fire-retardant polyester fibre HOY, preparation process is as follows：
(1) melt blending, will the obtained end organic phosphorous-thioesters compound of sulfydryl of dried embodiment 1 and PET cut into slices into
Row is mixed to get premix, and the organic phosphorous-thioesters compound of its middle-end sulfydryl is 3 with the mass ratio of PET sections: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, dried flame retardant polyester section is obtained resistance through measuring, extruding, cool down, oil with high-speed winding
Retardant polyester fiber HOY, the technological parameter of melt spinning is：
Extrusion temperature：290℃；
Chilling temperature：20℃；
High-speed winding speed：5000m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre HOY is 34%, and filament number is 0.3dtex, fracture
Intensity is 3.0cN/dtex, and elongation at break is 46%.
Embodiment 8
A kind of fire-retardant polyester fibre HOY, preparation process is as follows：
(1) melt blending, will the obtained end organic phosphorous-thioesters compound of sulfydryl of dried embodiment 2 and PET cut into slices into
Row is mixed to get premix, and the organic phosphorous-thioesters compound of its middle-end sulfydryl is 5 with the mass ratio of PET sections: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, dried flame retardant polyester section is obtained resistance through measuring, extruding, cool down, oil with high-speed winding
Retardant polyester fiber HOY, the technological parameter of melt spinning is：
Extrusion temperature：292℃；
Chilling temperature：21℃；
High-speed winding speed：5400m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre HOY is 34.3%, and filament number is 0.8dtex, is broken
Resistance to spalling is 3.2cN/dtex, and elongation at break is 48%.
Embodiment 9
A kind of fire-retardant polyester fibre HOY, preparation process is as follows：
(1) melt blending, will the obtained end organic phosphorous-thioesters compound of sulfydryl of dried embodiment 3 and PET cut into slices into
Row is mixed to get premix, and the organic phosphorous-thioesters compound of its middle-end sulfydryl is 7.5 with the mass ratio of PET sections:92.5, will be pre-
Section is obtained flame retardant polyester section to batch mixing after melt blending under the conditions of 259 DEG C in the double screw extruder；
(2) melt spinning, dried flame retardant polyester section is obtained resistance through measuring, extruding, cool down, oil with high-speed winding
Retardant polyester fiber HOY, the technological parameter of melt spinning is：
Extrusion temperature：294℃；
Chilling temperature：22℃；
High-speed winding speed：5800m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre HOY is 34.8%, and filament number is 1.0dtex, is broken
Resistance to spalling is 3.3cN/dtex, and elongation at break is 50%.
Embodiment 10
A kind of fire-retardant polyester fibre HOY, preparation process is as follows：
(1) melt blending, will the obtained end organic phosphorous-thioesters compound of sulfydryl of dried embodiment 4 and PET cut into slices into
Row is mixed to get premix, and the organic phosphorous-thioesters compound of its middle-end sulfydryl is 8.5 with the mass ratio of PET sections:91.5, will be pre-
Section is obtained flame retardant polyester section to batch mixing after melt blending under the conditions of 261 DEG C in the double screw extruder；
(2) melt spinning, dried flame retardant polyester section is obtained resistance through measuring, extruding, cool down, oil with high-speed winding
Retardant polyester fiber HOY, the technological parameter of melt spinning is：
Extrusion temperature：296℃；
Chilling temperature：23℃；
High-speed winding speed：6200m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre HOY is 35.6%, and filament number is 1.3dtex, is broken
Resistance to spalling is 3.5cN/dtex, and elongation at break is 52%.
Embodiment 11
A kind of fire-retardant polyester fibre HOY, preparation process is as follows：
(1) melt blending, will the obtained end organic phosphorous-thioesters compound of sulfydryl of dried embodiment 5 and PET cut into slices into
Row is mixed to get premix, and the organic phosphorous-thioesters compound of its middle-end sulfydryl is 9 with the mass ratio of PET sections: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, dried flame retardant polyester section is obtained resistance through measuring, extruding, cool down, oil with high-speed winding
Retardant polyester fiber HOY, the technological parameter of melt spinning is：
Extrusion temperature：298℃；
Chilling temperature：24℃；
High-speed winding speed：6600m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre HOY is 35.5%, and filament number is 1.8dtex, is broken
Resistance to spalling is 3.6cN/dtex, and elongation at break is 53%.
Embodiment 12
A kind of fire-retardant polyester fibre HOY, preparation process is as follows：
(1) melt blending, will the obtained end organic phosphorous-thioesters compound of sulfydryl of dried embodiment 6 and PET cut into slices into
Row is mixed to get premix, and the organic phosphorous-thioesters compound of its middle-end sulfydryl is 10 with the mass ratio of PET sections: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, dried flame retardant polyester section is obtained resistance through measuring, extruding, cool down, oil with high-speed winding
Retardant polyester fiber HOY, the technological parameter of melt spinning is：
Extrusion temperature：300℃；
Chilling temperature：25℃；
High-speed winding speed：7000m/min.
The limited oxygen index of final obtained fire-retardant polyester fibre HOY is 36.8%, and filament number is 2.0dtex, is broken
Resistance to spalling is 3.8cN/dtex, and elongation at break is 54%.
Claims (10)
1. the preparation method of the organic phosphorous-thioesters compound of a kind of end sulfydryl, it is characterized in that, the organic phosphorous-thioesters of end sulfydryl
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 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 monocarboxylic acid containing sulfydryl and dihydroxylic alcohols with 1:1 mixed in molar ratio, adds catalyst, in inert gas shielding
With melt condensation reaction is carried out under conditions of mechanical agitation, obtain one end for sulfydryl, the other end for hydroxyl DADA；It is described organic
Sulfydryl is different with the reactivity of carboxylic acid group in monocarboxylic acid containing sulfydryl；
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 holding the organic phosphorous-thioesters compound of sulfydryl.
2. a kind of preparation method of the organic phosphorous-thioesters compound of end sulfydryl 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 phosphorous-thioesters compound of end sulfydryl according to claim 1, it is characterised in that institute
State organic monocarboxylic structural formula containing sulfydryl as follows：
The dihydroxylic alcohols is ethylene glycol, propane diols or 1,4- butanediols.
4. a kind of preparation method of the organic phosphorous-thioesters compound of end sulfydryl 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 monocarboxylic acid containing sulfydryl 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 phosphorous-thioesters compound of end sulfydryl 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 phosphorous-thioesterification of end sulfydryl obtained in the preparation method as described in any one of Claims 1 to 5
Thing, it is characterized in that：Organic phosphorous-thioesters the compound of end sulfydryl is solid-state carboxylate, the organic phosphorous-thioesterification of end sulfydryl
The molecular structural formula of thing is as follows：
In formula,The segment between the quaternary carbon C and R of the organic phosphorous-thioesters compound molecular center of end sulfydryl is represented, in segment-
CH2- be connected with the quaternary carbon C of carboxylate molecular center, concrete structure formula is as follows：
The R is that end group is the long-chain of sulfydryl；
The total content of P elements and element sulphur is 12.4~13.13wt% in the organic phosphorous-thioesters compound molecule of end sulfydryl.
7. the organic phosphorous-thioesters compound of a kind of end sulfydryl according to claim 6, it is characterised in that the end group is mercapto
The long-chain of base is following structure：
Wherein, n=2,3,4.
8. the organic phosphorous-thioesters compound of a kind of end sulfydryl according to claim 6, it is characterised in that the end sulfydryl has
Machine is phosphorous-and the molecular weight of thioesters compound is 1920~2032g/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 HOY as obtained in holding sulfydryl organic phosphorous-thioesters compound as claimed in claim 6,
It is characterized in that, the preparation process of fire-retardant polyester fibre HOY is as follows：
(1) melt blending, the organic phosphorous-thioesters compound of dried end sulfydryl 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 obtained fire-retardant gathering through measuring, extruding, cool down, oil with high-speed winding
Ester fiber HOY.
10. fire-retardant polyester fibre HOY according to claim 9, it is characterised in that the melt blending is in twin-screw
Carried out in extruder, the organic phosphorous-thioesters compound of end sulfydryl 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：290~300 DEG C；
Chilling temperature：20~25 DEG C；
High-speed winding speed：5000~7000m/min；
Limited oxygen index >=34% of described fire-retardant polyester fibre HOY, filament number be 0.3~2.0dtex, fracture strength >=
3.0cN/dtex, elongation at break is 50.0 ± 4.0%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710030664.6A CN106835340B (en) | 2017-01-16 | 2017-01-16 | A kind of organic phosphorous-thioesters compound of end sulfydryl and preparation method thereof and fire-retardant polyester fibre HOY as made from it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710030664.6A CN106835340B (en) | 2017-01-16 | 2017-01-16 | A kind of organic phosphorous-thioesters compound of end sulfydryl and preparation method thereof and fire-retardant polyester fibre HOY as made from it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106835340A true CN106835340A (en) | 2017-06-13 |
| CN106835340B CN106835340B (en) | 2018-12-04 |
Family
ID=59124828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710030664.6A Active CN106835340B (en) | 2017-01-16 | 2017-01-16 | A kind of organic phosphorous-thioesters compound of end sulfydryl and preparation method thereof and fire-retardant polyester fibre HOY as made from it |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106835340B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112795998A (en) * | 2020-12-28 | 2021-05-14 | 湖南美莱珀科技发展有限公司 | Preparation method of non-intrinsic flame-retardant high-strength polyester industrial yarn |
| CN114773241A (en) * | 2022-04-20 | 2022-07-22 | 益丰新材料股份有限公司 | Continuous synthesis method of mercaptocarboxylic ester |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1888013A (en) * | 2006-06-20 | 2007-01-03 | 东华大学 | Dicyclic phosphonate fire retardant and its synthesis |
| WO2008132111A1 (en) * | 2007-04-26 | 2008-11-06 | Basf Se | Flame-retardant thermoplastic molding compositions |
| CN101921407A (en) * | 2010-08-17 | 2010-12-22 | 东华大学 | Bromine-containing pentaerythritol phosphoester retardant and preparation method thereof |
| CN105778094A (en) * | 2016-03-08 | 2016-07-20 | 深圳职业技术学院 | Halogen-free flame-retardant optical resin |
-
2017
- 2017-01-16 CN CN201710030664.6A patent/CN106835340B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1888013A (en) * | 2006-06-20 | 2007-01-03 | 东华大学 | Dicyclic phosphonate fire retardant and its synthesis |
| WO2008132111A1 (en) * | 2007-04-26 | 2008-11-06 | Basf Se | Flame-retardant thermoplastic molding compositions |
| CN101921407A (en) * | 2010-08-17 | 2010-12-22 | 东华大学 | Bromine-containing pentaerythritol phosphoester retardant and preparation method thereof |
| CN105778094A (en) * | 2016-03-08 | 2016-07-20 | 深圳职业技术学院 | Halogen-free flame-retardant optical resin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112795998A (en) * | 2020-12-28 | 2021-05-14 | 湖南美莱珀科技发展有限公司 | Preparation method of non-intrinsic flame-retardant high-strength polyester industrial yarn |
| CN112795998B (en) * | 2020-12-28 | 2022-05-31 | 湖南美莱珀科技发展有限公司 | Preparation method of non-intrinsic flame-retardant high-strength polyester industrial yarn |
| CN114773241A (en) * | 2022-04-20 | 2022-07-22 | 益丰新材料股份有限公司 | Continuous synthesis method of mercaptocarboxylic ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106835340B (en) | 2018-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106866740B (en) | A kind of carboxylate and preparation method thereof | |
| CN106810579B (en) | A kind of organic containing phosphorus-nitrogen carboxylate of terminal hydroxy group and preparation method thereof and fire-retardant polyester fibre FDY as made from it | |
| CN102863611B (en) | Azobenzene structure based high-temperature self-cross-linked expanded flame-retardant anti-dripping copolyester and preparation method thereof | |
| CN101200820B (en) | Method for preparing flame-proof polyester fiber | |
| CN102199807B (en) | Method for producing phosphorus copolymerized flame-retarding terylene high-strength industrial yarns | |
| CN101851811B (en) | Method for preparing flame-retardant and anti-dripping polyester fiber | |
| CN103232596B (en) | Aliphatic-polyamide-modified copolyester, aliphatic-polyamide-modified copolyester fiber, and preparation methods thereof | |
| CN102702496A (en) | Preparation method of high-viscosity, wear-resistant, antistatic and flame-retardant polyester | |
| CN106835340B (en) | A kind of organic phosphorous-thioesters compound of end sulfydryl and preparation method thereof and fire-retardant polyester fibre HOY as made from it | |
| JP3897138B2 (en) | Flame retardant polyester resin composition and method for producing the same | |
| CN101407577A (en) | Low-melting point phosphor-containing flame-retardant copolyester and preparation thereof | |
| DE10121542A1 (en) | Composition and process for the production of polyester | |
| CN102586907B (en) | Production method of inflaming retarding hollow polyster fiber | |
| CN106831877B (en) | A kind of end group is organic phosphorus esters compound of acidic-group and preparation method thereof and 6 fabric of Flameproof polyamide as made from it | |
| CN104640928B (en) | Polyethylene terephthalate compositions, its manufacture method | |
| CN101864612B (en) | Preparation method of cationic dyeable halogen-free flame retardant polyester fiber | |
| CN1260269C (en) | Modified polyester and process for continuously producing same | |
| CN106866516A (en) | A kind of end group is organic nitrogen-containing carboxylate of carboxylic acid group and preparation method thereof | |
| CN1253486C (en) | Modified polyester and preparing method thereof | |
| CN112280022A (en) | Preparation method and application of composition for heavy metal-free low-melting-point polyester | |
| CN106810578B (en) | A kind of organic containing phosphorus-nitrogen of end sulfydryl-thioesters compound and preparation method thereof and fire-retardant polyester fibre POY as made from it | |
| CN106831552B (en) | A kind of end group is organic nitrogen-containing-thioesters compound and preparation method thereof of sulfydryl | |
| CN106810680A (en) | A kind of organic phosphorus-nitrogen containing thioesters compound of terminal hydroxy group and preparation method thereof and by its obtained flame-proof cotton fabric | |
| CN101469059A (en) | Preparation of flame-retardant copolymerization modified poly(trimethylene terephthalate) | |
| CN106866517B (en) | A kind of end group is organic nitrogen-containing-thioesters compound and preparation method thereof of carboxylic acid group |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |