CN102888085A - Additive type phosphorus phenanthrene oxa-flame retardant and preparation method thereof - Google Patents
Additive type phosphorus phenanthrene oxa-flame retardant and preparation method thereof Download PDFInfo
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- CN102888085A CN102888085A CN2012104421301A CN201210442130A CN102888085A CN 102888085 A CN102888085 A CN 102888085A CN 2012104421301 A CN2012104421301 A CN 2012104421301A CN 201210442130 A CN201210442130 A CN 201210442130A CN 102888085 A CN102888085 A CN 102888085A
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Abstract
The invention discloses an additive type phosphorus phenanthrene oxa-flame retardant and a preparation method thereof. The chemical name of the additive type phosphorus phenanthrene oxa-flame retardant is poly-(10-taconic acid gylcol ester-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide). The preparation method comprises the following steps of: firstly carrying out a reaction on DOPO, itaconic acid and ethylene glycol to generate a monomer midbody 10-taconic acid gylcol ester-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; and polymerizing the reacting midbody at high temperature under the function of catalyst to obtain a target product. The additive type phosphorus phenanthrene oxa-flame retardant provided by the invention is applicable to various high molecular materials with higher processing temperature such as linear polyester, fiber, polyamide, polyurethane and the like; and the preparation method is free from halogen, environment-friendly, simple in operation process, easy to control, high in yield, good in product repeatability, and less in impurity, wherein the product yield can be 98.5%-99.9%, and the production cost can be reduced.
Description
Technical field
The present invention relates to a kind of fire retardant, be specifically related to luxuriant and rich with fragrance oxa-fire retardant of a kind of addition type phosphorus and preparation method thereof.
Background technology
Along with the rapid emergence of polymer material science, macromolecular material is widely used in the mankind's productive life, and is also more and more by the fire that ignites and cause by it, so the flame retardant properties of macromolecular material obtains people's extensive concern.Japan and Germany etc. have carried out very deep research, and China also conducts extensive research discussion in this field, also obtained some considerable achievements.Particularly along with the day by day minimizing of bromine resource, having relatively better, the fire retardant of the phosphorus series of flame retardant properties is developed rapidly, DOPO and derivative thereof can be by the methods of copolymerization, the compound that will contain ignition-proof element is introduced high polymer main chain, have resistance combustion temperature height, toxicity low, to characteristics such as the performance impact of macromolecular material are less, so this type of macromolecular material fire retardant progressively obtains client's approval and is widely used.
At present, document DE2816100C2 discloses a kind of fire retardant and has obtained by the adduct of DOPO or DOPO derivative and methylene-succinic acid and the polycondensation of polyvalent alcohol, and molecular weight is 1000～20000g/mol, and phosphorus content is 5.3～8.5 % by weight.But because this technical costs is higher, process is complicated, operational difficulty, therefore be difficult to realize suitability for industrialized production.Publication number is the Chinese patent of CN 101108864A, the synthetic method that discloses DOPO with and the preparation method of derivative DDP-EG, wherein DOPO, methylene-succinic acid, ethylene glycol are dewatered by the molar ratio heating of 1:1:3 and obtain flaxen viscous liquid DDP-EG.But this product is reactive flame retardant, in application facet significant limitation is arranged, and only is only applicable to several exotic materialss, scope of application relative narrower.
Summary of the invention
Technical problem to be solved by this invention provides luxuriant and rich with fragrance oxa-fire retardant of a kind of addition type phosphorus and preparation method thereof, and its preparation technology is simple, and can be applied to the fire-retardant of multiple macromolecular material, thereby eliminates defective in the above-mentioned background technology.
For solving the problems of the technologies described above, technical scheme of the present invention is:
The luxuriant and rich with fragrance oxa-fire retardant of a kind of addition type phosphorus has following chemical structural formula:
(co-DOPO-BDA)
Wherein n is 10～20.
The chemistry of above-claimed cpd poly-(10-methylene-succinic acid glycol ester-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) by name is referred to as co-DOPO-BDA.
The main raw material of co-DOPO-BDA is DOPO(9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound), methylene-succinic acid and ethylene glycol, first reaction generates monomer intermediate 10-methylene-succinic acid glycol ester-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; Reaction intermediate high temperature polymerization under catalyst action obtains target product: poly-(10-methylene-succinic acid glycol ester-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), the appropriate change reaction conditions obtains the polymerization degree of needs according to demand.
As a kind of improvement, it is as follows to prepare described co-DOPO-BDA chemical reaction:
The preparation method of the luxuriant and rich with fragrance oxa-fire retardant of addition type phosphorus comprises the steps:
(1) is that 1:1:1.05～1.5 mix with methylene-succinic acid, ethylene glycol according to mol ratio with DOPO, and in 120 ℃～160 ℃ lower dissolvings, distills 4h～8h 180 ℃～220 ℃ lower atmospheric pressure reflux behind the dissolve complete, to remove the water that generates in the dereaction;
(2) in the solution with the disposable adding step of catalyzer (1), at 210 ℃～230 ℃ second vacuum distilling 2h～3h, distill out water residual in the solution of step (1);
(3) at the solution 4h～12h of 240 ℃～280 ℃ lower vacuum distilation steps (2), make the monomer intermediate polymerization of product, after finishing, polymerization obtains product.
After reaction is finished, emit while hot product, make its curing, with the product section, packing gets final product.
As a kind of improvement, the preferred 1:1:1.1 of the mol ratio of described DOPO and methylene-succinic acid, ethylene glycol～1.2.
As a kind of improvement, in the described step (1), preferred 200 ℃～210 ℃ of reflux distillation temperature.
As a kind of improvement, in the described step (1), preferred 5h～6h of the time of reflux distillation.
As a kind of improvement, in the described step (2), described catalyzer is one or both in antimonous oxide, butyl (tetra) titanate, Tetrabutyl amonium bromide, the triethyl benzyl ammonia chloride.
As further improvement, the preferred butyl (tetra) titanate of described catalyzer.
As further improvement, the mol ratio of described DOPO and catalyzer is 1:0.05～1.0.
As a kind of improvement, in the described step (2), preferred 220 ℃ of the temperature of partial vacuum underpressure distillation, the partial vacuum refers to-0.04～-0.05MPa.
As a kind of improvement, in the described step (3), preferred 250 ℃～260 ℃ of the temperature of vacuum distillation, vacuum refer to-0.095～-0.096MPa.
As a kind of improvement, in the described step (3), the preferred 6h～8h of time of vacuum distillation.
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
The luxuriant and rich with fragrance oxa-fire retardant of addition type phosphorus provided by the invention, that the DOPO derivative is further processed the superpolymer that obtains, its product processing temperature is higher, flame retardant effect is also better, be applicable to multiple macromolecular material, be specially adapted to the fire-retardant finish of the higher macromolecular material of the multiple processing temperatures such as linear polyester, fiber, polymeric amide and urethane.And gentle in the use procedure stable reaction, without waste water, accomplished environmental protection.
The characteristics such as co-DOPO-BDA is as New-type halide-free phosphorus flame retardant DOPO derivative, and high in the thermostability that is possessing DOPO, seepage discharge is few, and processing characteristics is excellent, and environmental protection such as does not corrode at the advantage, and it is good also to have anti-dropping liquid performance, and devitrification resistance is good.Co-DOPO-BDA belongs to phosphorus flame retardant, have fire-retardant and the plasticising double effects, it is non-halogen that fire retardant is realized fully, improves the flowing property in the plastic shaping, resistates after suppressing to burn, poisonous gas and the corrosive gases of generation lack than halogen flame.
Preparation method provided by the invention, halogen-free environmental, operating process is easy, and is easy to control, and output is high, and product yield can reach 98.5%～99.9%, good reproducibility in the production, impurity is few, has reduced production cost.
Figure of description
Fig. 1 is the DSC graphic representation of product of the present invention.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
(1) 0.4molDOPO, 0.4mol methylene-succinic acid and 0.42mol ethylene glycol are mixed in the input reactor, be warming up to 120 ℃ of lower dissolvings, obtain clear solution behind the dissolve complete and stir, then at 180 ℃ of lower atmospheric pressure reflux distillation 4h～8h, except the water that generates in the dereaction;
(2) with the 0.02mol butyl (tetra) titanate as catalyzer, in the solution of disposable adding step (1), be-second vacuum distilling of 0.04MPa 2h to distill out water residual in the solution of step (1) at 210 ℃, vacuum tightness;
(3) at 240 ℃, vacuum tightness be-0.095MPa under the solution 4h of vacuum distilation steps (2), make the monomer intermediate polymerization of product, obtain product after polymerization is finished;
After reaction is finished, emit while hot product, make its curing, with the product section, packing gets final product.
The DOPO derivative of the present invention's preparation, as follows through the technology for detection index:
Product is amber crystal, fusing point: 76.2～82.1 ℃, product yield is 98.99%.
Embodiment 2
(1) 0.4molDOPO, 0.4mol methylene-succinic acid and 0.6mol ethylene glycol are mixed in the input reactor, be warming up to 160 ℃ of lower dissolvings, obtain clear solution behind the dissolve complete to stir, then at 220 ℃ of lower atmospheric pressure reflux distillation 8h, except the water that generates in the dereaction;
(2) with 0.4mol antimonous oxide and butyl (tetra) titanate mixture as catalyzer, in the solution of disposable adding step (1), be-second vacuum distilling of 0.05MPa 3h to distill out water residual in the solution of step (1) at 230 ℃, vacuum tightness;
(3) at 280 ℃, vacuum tightness be-0.096MPa under the solution 12h of vacuum distilation steps (2), make the monomer intermediate polymerization of product, obtain product after polymerization is finished;
After reaction is finished, emit while hot product, make its curing, with the product section, packing gets final product.
The DOPO derivative of the present invention's preparation, as follows through the technology for detection index:
Product is amber crystal, fusing point: 75.4～82.2 ℃, product yield is 99.33%.
Embodiment 3
(1) 0.4molDOPO, 0.4mol methylene-succinic acid and 0.44mol ethylene glycol are mixed in the input reactor, be warming up to 140 ℃ of lower dissolvings, obtain clear solution behind the dissolve complete and stir, then at 200 ℃ of lower atmospheric pressure reflux distillation 5h, except the water that generates in the dereaction;
(2) with the 0.3mol triethyl benzyl ammonia chloride as catalyzer, in the solution of disposable adding step (1), be-second vacuum distilling of 0.045MPa 2h～3h to distill out water residual in the solution of step (1) at 220 ℃, vacuum tightness;
(3) at 260 ℃, vacuum tightness be-0.096MPa under the solution 8h of vacuum distilation steps (2), make the monomer intermediate polymerization of product, obtain product after polymerization is finished;
After reaction is finished, emit while hot product, make its curing, with the product section, packing gets final product.
The DOPO derivative of the present invention's preparation, as follows through the technology for detection index:
Product is amber crystal, fusing point: 81.5～86.4 ℃, product yield is 99.93%.
Embodiment 4
(1) 0.4molDOPO, 0.4mol methylene-succinic acid and 0.48mol ethylene glycol are mixed in the input reactor, be warming up to 150 ℃ of lower dissolvings, obtain clear solution behind the dissolve complete and stir, then at 210 ℃ of lower atmospheric pressure reflux distillation 4h～8h, except the water that generates in the dereaction;
(2) with the 0.3mol butyl (tetra) titanate as catalyzer, in the solution of disposable adding step (1), be-second vacuum distilling of 0.048MPa 3h to distill out water residual in the solution of step (1) at 220 ℃, vacuum tightness;
(3) at 250 ℃, vacuum tightness be-0.096MPa under the solution 10h of vacuum distilation steps (2), make the monomer intermediate polymerization of product, obtain product after polymerization is finished;
After reaction is finished, emit while hot product, make its curing, with the product section, packing gets final product.
The DOPO derivative of the present invention's preparation, as follows through the technology for detection index:
Product is amber crystal, fusing point: 81.5～86.4 ℃, product yield is 99.87%.
Fig. 1 is the DSC graphic representation of product.Find out conforming to of product spectrogram tendency and high dimeric molecule material crystal habit spectrogram tendency by DSC graphic representation test result, and the first fusing point of product is that 81.52 ℃, whole fusing point are 87.64 ℃ as seen from the figure, fusing point is 84.68 ℃, its temperature of fusion narrow range, the polymerization effect that product is described is good, is a kind of xln of molecular weight distribution relative narrower.
The comparative example
The comparative example adopts the method among the documents 101108864A to be prepared.
0.4molDOPO, 1.2mol ethylene glycol are added in the reactor, be heated to 120 ℃, stir, add again the 0.4mol methylene-succinic acid, be heated to 180 ℃, and minute water outlet, reaction 3h.
The product that obtains is faint yellow viscous liquid, is DDP-EG after testing.
In traditional technology, most of producers adopt the solid materials addition manner, DDP-EG is that the liquid producer of thickness adds and to need on the use-pattern to improve, to using producer to bring inconvenience, and DDP-EG is the fire retardant of response type, use limitation larger, only can be applicable to several resin materials with reactive behavior; Product co-DOPO-BDA is solid, be convenient to add use, and the scope of application is wider, can directly add various Plastic Resin master batches to, and is easy to use.
The present invention is not limited to above-mentioned embodiment, and all are based on technical conceive of the present invention, and the structural improvement of having done all falls among protection scope of the present invention.
Claims (10)
1. the luxuriant and rich with fragrance oxa-fire retardant of an addition type phosphorus is characterized in that: have following chemical structural formula:
(co-DOPO-BDA)
Wherein n is 10～20.
2. the preparation method of the luxuriant and rich with fragrance oxa-fire retardant of addition type phosphorus as claimed in claim 1 is characterized in that: comprise the steps:
(1) is that 1:1:1.05～1.5 mix with methylene-succinic acid, ethylene glycol according to mol ratio with DOPO, and in 120 ℃～160 ℃ lower dissolvings, distills 4h～8h 180 ℃～220 ℃ lower atmospheric pressure reflux behind the dissolve complete;
(2) in the solution with the disposable adding step of catalyzer (1), at 210 ℃～230 ℃ second vacuum distilling 2h～3h;
(3) at the solution 4h～12h of 240 ℃～280 ℃ lower vacuum distilation steps (2), after finishing, polyreaction obtains product.
3. the preparation method of the luxuriant and rich with fragrance oxa-fire retardant of addition type phosphorus as claimed in claim 2, it is characterized in that: the mol ratio of described DOPO and methylene-succinic acid, ethylene glycol is 1:1:1.1～1.2.
4. the preparation method of the luxuriant and rich with fragrance oxa-fire retardant of addition type phosphorus as claimed in claim 2, it is characterized in that: in the described step (1), the atmospheric pressure reflux distillation temperature is 200 ℃～210 ℃, and the time is 5h～6h.
5. the preparation method of the luxuriant and rich with fragrance oxa-fire retardant of addition type phosphorus as claimed in claim 2, it is characterized in that: in the described step (2), described catalyzer is one or both in antimonous oxide, butyl (tetra) titanate, Tetrabutyl amonium bromide, the triethyl benzyl ammonia chloride.
6. the preparation method of the luxuriant and rich with fragrance oxa-fire retardant of addition type phosphorus as claimed in claim 5, it is characterized in that: described catalyzer is butyl (tetra) titanate.
7. such as the preparation method of claim 5 or the luxuriant and rich with fragrance oxa-fire retardant of 6 described addition type phosphorus, it is characterized in that: the mol ratio of DOPO and described catalyzer is 1:0.05～1.0.
8. the preparation method of the luxuriant and rich with fragrance oxa-fire retardant of addition type phosphorus as claimed in claim 2, it is characterized in that: in the described step (2), the temperature of partial vacuum underpressure distillation is 220 ℃, vacuum tightness is-0.04～-0.05MPa.
9. the preparation method of the luxuriant and rich with fragrance oxa-fire retardant of addition type phosphorus as claimed in claim 2, it is characterized in that: in the described step (3), the temperature of vacuum distillation is 250 ℃～260 ℃, vacuum tightness is-0.095～-0.096MPa.
10. the preparation method of the luxuriant and rich with fragrance oxa-fire retardant of addition type phosphorus as claimed in claim 9, it is characterized in that: in the described step (3), the time of vacuum distillation is 6h～8h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772740A (en) * | 2014-01-16 | 2014-05-07 | 寿光卫东化工有限公司 | Phosphorus-containing flame retardant and preparation method thereof |
| CN103833947A (en) * | 2014-02-21 | 2014-06-04 | 华东理工大学 | Synthesis and application of reaction type halogen-free phosphorus-containing flame retardant for polyurethane |
| CN104419003A (en) * | 2013-09-04 | 2015-03-18 | 广州熵能创新材料股份有限公司 | Phosphaphenanthrene polyamide flame retardant and preparation and application thereof |
| CN105237674A (en) * | 2015-11-23 | 2016-01-13 | 兰州理工大学 | Method for preparing phosphorus-containing flame-retardant acrylic resin |
| DE102015112592A1 (en) * | 2015-07-31 | 2017-02-02 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Flame-resistant polyamide as the reaction product of a lactam, a process for its preparation and its use |
| CN110283562A (en) * | 2019-06-17 | 2019-09-27 | 广东莱尔新材料科技股份有限公司 | A kind of FFC wire rod hot melt adhesive film of the resistance to combustion of no antimony and preparation method thereof |
| CN112812285A (en) * | 2020-12-28 | 2021-05-18 | 湖南美莱珀科技发展有限公司 | Macromolecular flame retardant and preparation method and application thereof |
| CN114933754A (en) * | 2022-05-19 | 2022-08-23 | 中瀚新材料科技有限公司 | High-resistance halogen-free flame-retardant cable sheath material and preparation method thereof |
| CN115894903A (en) * | 2022-11-29 | 2023-04-04 | 浙江理工大学 | Copolymerized flame-retardant polyamide 66 and preparation method thereof |
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| CN101151320A (en) * | 2005-03-31 | 2008-03-26 | 钟渊化学工业株式会社 | Flame retardant polyester resin composition |
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| CN101151320A (en) * | 2005-03-31 | 2008-03-26 | 钟渊化学工业株式会社 | Flame retardant polyester resin composition |
Cited By (12)
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| CN104419003A (en) * | 2013-09-04 | 2015-03-18 | 广州熵能创新材料股份有限公司 | Phosphaphenanthrene polyamide flame retardant and preparation and application thereof |
| CN104419003B (en) * | 2013-09-04 | 2018-09-11 | 广州熵能创新材料股份有限公司 | One kind fire retardant of polyamide containing phospho hetero phenanthrene and its preparation and application |
| CN103772740A (en) * | 2014-01-16 | 2014-05-07 | 寿光卫东化工有限公司 | Phosphorus-containing flame retardant and preparation method thereof |
| CN103833947A (en) * | 2014-02-21 | 2014-06-04 | 华东理工大学 | Synthesis and application of reaction type halogen-free phosphorus-containing flame retardant for polyurethane |
| DE102015112592A1 (en) * | 2015-07-31 | 2017-02-02 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Flame-resistant polyamide as the reaction product of a lactam, a process for its preparation and its use |
| CN105237674A (en) * | 2015-11-23 | 2016-01-13 | 兰州理工大学 | Method for preparing phosphorus-containing flame-retardant acrylic resin |
| CN110283562A (en) * | 2019-06-17 | 2019-09-27 | 广东莱尔新材料科技股份有限公司 | A kind of FFC wire rod hot melt adhesive film of the resistance to combustion of no antimony and preparation method thereof |
| CN110283562B (en) * | 2019-06-17 | 2022-02-01 | 广东莱尔新材料科技股份有限公司 | Antimony-free flame-retardant hot melt adhesive film for FFC wire and preparation method thereof |
| CN112812285A (en) * | 2020-12-28 | 2021-05-18 | 湖南美莱珀科技发展有限公司 | Macromolecular flame retardant and preparation method and application thereof |
| CN114933754A (en) * | 2022-05-19 | 2022-08-23 | 中瀚新材料科技有限公司 | High-resistance halogen-free flame-retardant cable sheath material and preparation method thereof |
| CN114933754B (en) * | 2022-05-19 | 2023-12-29 | 中瀚新材料科技有限公司 | High-resistance halogen-free flame-retardant cable sheath material and preparation method thereof |
| CN115894903A (en) * | 2022-11-29 | 2023-04-04 | 浙江理工大学 | Copolymerized flame-retardant polyamide 66 and preparation method thereof |
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