CN106496536A - The preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate - Google Patents
The preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate Download PDFInfo
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- CN106496536A CN106496536A CN201611043125.8A CN201611043125A CN106496536A CN 106496536 A CN106496536 A CN 106496536A CN 201611043125 A CN201611043125 A CN 201611043125A CN 106496536 A CN106496536 A CN 106496536A
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- CN
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- Prior art keywords
- fire retardant
- polyethylene terephthalate
- preparation
- containing phosphorus
- phosphorus silicon
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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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to technical field of function materials, and in particular to a kind of preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate.The preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate, weighs p-phthalic acid, by p-phthalic acid and ethylene glycol mixing input reactor, catalyst, heat stabilizer, anti-ether agent, fire retardant succinic acid is added together, is sufficiently stirred for；Nitrogen is esterified, and when the water yield for distilling is not less than the 95% of theoretical amount, reaction terminates；Start to vacuumize, when polycondensation power is raised to 150 ~ 170 W, reaction terminates；Through discharging, pelletizing and drying, the copolyester section of difference phosphorus content is obtained；Using miniature blending instrument by nanoscale SiO2The fire retardant polyethylene terephthalate of containing phosphorus silicon is prepared with copolyester section blending.After the present invention adds fire retardant succinic acid, the initial decomposition temperature range of decrease is less than 5 DEG C, and most degradation speed reduces, and illustrates that the presence of P elements inhibits the degraded of polyethylene terephthalate strand.
Description
Technical field
The present invention relates to technical field of function materials, and in particular to a kind of containing phosphorus silicon fire retardant polyethylene terephthalate
Preparation method.
Background technology
Polyethylene terephthalate is the portion of a kind of chemical-resistant reagent, good heat endurance, high intensity and good spinnability
Divide crystalline polymer.Pet fiber is widely used in every field as the first big synthetic fibers, and
Which has become the fifth-largest engineering plastics after nylon, Merlon, polyformaldehyde, polyphenylene oxide as thermoplastic resin.So
And, due to making which the characteristics of polyethylene terephthalate is inflammable in some key areas such as automobile industry, electronic product, resistance
The application of combustion protective garment etc. is restricted.Halogen-free flame retardants currently used for polyethylene terephthalate is mainly phosphorus system
Fire retardant, but have the shortcomings that fire retardant polyethylene terephthalate molten drop causes second-time burning.Therefore, most of in recent years
Researcher is devoted to the exploitation of flame-retardant and anti-dripping polyethylene terephthalate.
Synthesized fire retardant on the market, then in tetraethyl orthosilicate (TEOS) sol system with its cohydrolysis, obtain molecule
In fire retardant simultaneously containing two kinds of elements of phosphorus silicon, be coated on cotton fiber and reached fire-retardant effect.There is researcher with altogether
Poly- mode induces one phosphonium flame retardant, then introduces inorganic anti-dropping particle in the way of in-situ polymerization.For example, the synthesis such as Guo Deming
Double (ethoxy) bisphenol-As (BHEEB) of modified monomer, to be copolymerized to together with phosphorous copoly type monomer succinic acid (succinic acid) poly- right
In PET strand, modified polyethylene terephthalate limited oxygen index (LOI) brings up to
37.00%, vertical combustion reaches V-O grades.Wang Deyi etc. is obtained phosphorous nano composite material, LOI using the mode of in-situ polymerization
32.6% is brought up to, vertical combustion reaches V-O grades.Additionally, the method for the combined polymerization that compares, blending method is relatively simple.
Content of the invention
It is contemplated that proposing a kind of preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate.
Technical program of the present invention lies in：
The preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate, comprises the steps：
（1）The preparation of phosphorous copolyester
Esterification Stage：1000 ~ 1100 g of p-phthalic acid is weighed, by p-phthalic acid and ethylene glycol mixing input reaction
Kettle, while catalyst, heat stabilizer, anti-ether agent, fire retardant succinic acid are added together, is sufficiently stirred for, and is obtained finely dispersed
Slurries；It is filled with the protection of 0.2 ~ 0.5MPa nitrogen to be esterified, when the water yield distilled from esterification condensing unit is not less than reason
Stoichiometric 95% when, reaction terminates, 30 ~ 40 min of normal pressure esterification or so；
Polycondensation phase：Rise high-temperature to 280 ~ 300 DEG C, start simultaneously at and vacuumize, be evacuated within 30 ~ 45 min 100Pa with
Under, when polycondensation power is raised to 150 ~ 170 W, reaction terminates；Through discharging, pelletizing and drying, the copolymerization of difference phosphorus content is obtained
Ester is cut into slices；
（2）Phosphorous copolyester and SiO2The preparation of blend
Using miniature blending instrument by nanoscale SiO2It is blended with copolyester section, blending temperature is set to 260 DEG C, and screw speed is set to
70 ~ 100 r/min, prepare the fire retardant polyethylene terephthalate of containing phosphorus silicon.
The mol ratio of described p-phthalic acid and ethylene glycol is l：1.4.
230～240 DEG C of described esterification temperature, 2 ~ 2.5 h of esterification time, esterification pressures are 0.35～0.4MPa.
270～280 DEG C of described polycondensation reaction temperature, 50 ~ 60 Pa of vacuum.
Described blending adopts miniature blending instrument.
The method have technical effect that：
After the present invention adds fire retardant succinic acid, the initial decomposition temperature range of decrease is less than 5 DEG C, and most degradation speed reduces, explanation
The presence of P elements inhibits the degraded of polyethylene terephthalate strand.Under 800 DEG C of high temperature, phosphorus can be catalyzed rush
Enter into the formation of charcoal, and increase residual mass, and SiO2Non-degradable, further increase residual mass.
Specific embodiment
The preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate, comprises the steps：
Embodiment 1
（1）The preparation of phosphorous copolyester
Esterification Stage：P-phthalic acid 1000g is weighed, by p-phthalic acid and ethylene glycol mixing input reactor, while
Catalyst, heat stabilizer, anti-ether agent, fire retardant succinic acid are added together, is sufficiently stirred for, finely dispersed slurries are obtained；Fill
Enter the protection of 0.2 MPa nitrogen to be esterified, when the water yield distilled from esterification condensing unit is not less than the 95% of theoretical amount
When, reaction terminates, normal pressure esterification 30min or so；
Polycondensation phase：High-temperature is risen to 280 DEG C, is started simultaneously at and is vacuumized, below 100Pa is evacuated within 30 min, works as contracting
When poly- power is raised to 150 W, reaction terminates；Through discharging, pelletizing and drying, the copolyester section of difference phosphorus content is obtained；
（2）Phosphorous copolyester and SiO2The preparation of blend
Using miniature blending instrument by nanoscale SiO2It is blended with copolyester section, blending temperature is set to 260 DEG C, and screw speed is set to
70 r/min, prepare the fire retardant polyethylene terephthalate of containing phosphorus silicon.
Wherein, the mol ratio of described p-phthalic acid and ethylene glycol is l：1.4.230 DEG C of described esterification temperature, ester
2 h of change time, esterification pressures are 0.35MPa.270 DEG C of described polycondensation reaction temperature, 50 ~ 60 Pa of vacuum.Described blending
Using miniature blending instrument.
Embodiment 2
（1）The preparation of phosphorous copolyester
Esterification Stage：1100 g of p-phthalic acid is weighed, by p-phthalic acid and ethylene glycol mixing input reactor, while
Catalyst, heat stabilizer, anti-ether agent, fire retardant succinic acid are added together, is sufficiently stirred for, finely dispersed slurries are obtained；Fill
Enter the protection of 0.5MPa nitrogen to be esterified, when the water yield distilled from esterification condensing unit is not less than the 95% of theoretical amount
When, reaction terminates, 40 min of normal pressure esterification or so；
Polycondensation phase：High-temperature is risen to 300 DEG C, is started simultaneously at and is vacuumized, below 100Pa is evacuated within 45 min, works as contracting
When poly- power is raised to 170 W, reaction terminates；Through discharging, pelletizing and drying, the copolyester section of difference phosphorus content is obtained；
（2）Phosphorous copolyester and SiO2The preparation of blend
Using miniature blending instrument by nanoscale SiO2It is blended with copolyester section, blending temperature is set to 260 DEG C, and screw speed is set to
100 r/min, prepare the fire retardant polyethylene terephthalate of containing phosphorus silicon.
Wherein, the mol ratio of described p-phthalic acid and ethylene glycol is l：1.4.240 DEG C of described esterification temperature, ester
2.5 h of change time, esterification pressures are 0.4MPa.280 DEG C of described polycondensation reaction temperature, 60 Pa of vacuum.Described blending is adopted
With miniature blending instrument.
Claims (5)
1. the preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate, it is characterised in that：Comprise the steps：
（1）The preparation of phosphorous copolyester
Esterification Stage：1000 ~ 1100 g of p-phthalic acid is weighed, by p-phthalic acid and ethylene glycol mixing input reaction
Kettle, while catalyst, heat stabilizer, anti-ether agent, fire retardant succinic acid are added together, is sufficiently stirred for, and is obtained finely dispersed
Slurries；It is filled with the protection of 0.2 ~ 0.5MPa nitrogen to be esterified, when the water yield distilled from esterification condensing unit is not less than reason
Stoichiometric 95% when, reaction terminates, 30 ~ 40 min of normal pressure esterification or so；
Polycondensation phase：Rise high-temperature to 280 ~ 300 DEG C, start simultaneously at and vacuumize, be evacuated within 30 ~ 45 min 100Pa with
Under, when polycondensation power is raised to 150 ~ 170 W, reaction terminates；Through discharging, pelletizing and drying, the copolymerization of difference phosphorus content is obtained
Ester is cut into slices；
（2）Phosphorous copolyester and SiO2The preparation of blend
Using miniature blending instrument by nanoscale SiO2It is blended with copolyester section, blending temperature is set to 260 DEG C, and screw speed is set to
70 ~ 100 r/min, prepare the fire retardant polyethylene terephthalate of containing phosphorus silicon.
2. the preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate according to claim 1, it is characterised in that：
The mol ratio of described p-phthalic acid and ethylene glycol is l：1.4.
3. the preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate according to claim 1, it is characterised in that：
230～240 DEG C of described esterification temperature, 2 ~ 2.5 h of esterification time, esterification pressures are 0.35～0.4MPa.
4. the preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate according to claim 1, it is characterised in that：
270～280 DEG C of described polycondensation reaction temperature, 50 ~ 60 Pa of vacuum.
5. the preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate according to claim 1, it is characterised in that：
Described blending adopts miniature blending instrument.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201611043125.8A CN106496536A (en) | 2016-11-24 | 2016-11-24 | The preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate |
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| CN201611043125.8A CN106496536A (en) | 2016-11-24 | 2016-11-24 | The preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893274A (en) * | 2017-03-27 | 2017-06-27 | 山东本源晶体科技有限公司 | A kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material |
| CN108219283A (en) * | 2018-02-07 | 2018-06-29 | 枣庄市超钱塑业有限公司 | A kind of laser-light transparent amplification bag and preparation method thereof |
| WO2019127095A1 (en) * | 2017-12-27 | 2019-07-04 | 广东生益科技股份有限公司 | Phosphorous-containing silicon active ester and preparation method therefor, flame retardant resin composition, prepreg and metal foil-clad laminate |
| CN111020742A (en) * | 2019-12-19 | 2020-04-17 | 上海民航职业技术学院 | Anti-cutting thorn material and preparation method thereof |
-
2016
- 2016-11-24 CN CN201611043125.8A patent/CN106496536A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893274A (en) * | 2017-03-27 | 2017-06-27 | 山东本源晶体科技有限公司 | A kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material |
| CN106893274B (en) * | 2017-03-27 | 2018-03-30 | 山东本源晶体科技有限公司 | A kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material |
| WO2019127095A1 (en) * | 2017-12-27 | 2019-07-04 | 广东生益科技股份有限公司 | Phosphorous-containing silicon active ester and preparation method therefor, flame retardant resin composition, prepreg and metal foil-clad laminate |
| CN108219283A (en) * | 2018-02-07 | 2018-06-29 | 枣庄市超钱塑业有限公司 | A kind of laser-light transparent amplification bag and preparation method thereof |
| CN111020742A (en) * | 2019-12-19 | 2020-04-17 | 上海民航职业技术学院 | Anti-cutting thorn material and preparation method thereof |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170315 |
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| WD01 | Invention patent application deemed withdrawn after publication |