CN104592549A - Phosphorus-containing reaction-type fire retardant as well as synthesis method and application thereof - Google Patents
Phosphorus-containing reaction-type fire retardant as well as synthesis method and application thereof Download PDFInfo
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- CN104592549A CN104592549A CN201510054190.XA CN201510054190A CN104592549A CN 104592549 A CN104592549 A CN 104592549A CN 201510054190 A CN201510054190 A CN 201510054190A CN 104592549 A CN104592549 A CN 104592549A
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Abstract
The invention belongs to the technical field of organic chemical engineering, and particularly relates to a phosphorus-containing reaction-type fire retardant as well as a synthesis method and application thereof. The chemical name of the fire retardant is bis-9,10-dihydro-9-oxa-10-phosphonia-10-phenanthrene oxide-base (diDOPO-MDCA), the compound has two hydroxyl active sites and can be used as the fire retardant for resin reacting with the compound, the element phosphorus is introduced into a molecular structure of a macromolecular material in a form of a covalent bond, the fire resistance of the resin can be improved, and a non-toxic high-efficiency long fire retardant purpose can be realized. The production condition is simple, the product purity and yield are relatively high, and the after-treatment process is simple.
Description
Technical field
The present invention relates to field of chemical technology, specifically, relate to a kind of phosphorous reactive flame retardant, synthetic method and application thereof.
Background technology
21 century, macromolecular material is widely used in the life of industrial production and people, as fields such as automobile, electrical equipment, aerospace, Highrise buildings, indoor decorations.But most of macromolecular material has a fatal shortcoming: easily decompose under high temperature, burn; And the poisonous gas that during macromolecular material burning, decomposes is released, black smoke cause huge threat and injury especially to the life security of people.Therefore, flame retardance of polymer research receives the concern in the whole world.
At present, the fire-retardant research for macromolecular material is subject to the environmental protection of increasingly stringent and the impact of flame retardant regulation, and major part has taken leave of conventional halogen fire retardant, to burn the harm brought to overcome halogen.But, along with raising and the progress of flame-retardancy requirements, investigators more and more tend to research and develop a kind of response type halogen-free flame retardants, the deficiency avoiding using additive flame retardant to bring (with the problem such as matrix resin consistency is bad), these BACNs will have low rate of heat release, low raw cigarette, hypotoxicity and high flame retarding efficiency.(Synthesis of Naphthalene containing aralkyl novolac Epoxyresins for electronic Application [J] the .Macromolecular Materials and Engineering such as Ho T H, 2000,283:57-61) with terephthalaldehyde and 2,7-bisnaphthol, beta naphthal and phenol carry out condensation reaction respectively, obtain the phenolic resin of different structure respectively, then be obtained by reacting phenol aldehyde type epoxy resin through epichlorohydrin epoxy.Take phenol aldehyde type epoxy resin as flame retardant curing agent, the heat-proof combustion-resistant performance of gained cured article is obviously promoted.(NovelPhosphorus-containing Epoxy resins part1.Synthesis and Properties [J] .Polymer such as Lin C H, 2001,37:1869-1878) synthesize multi-epoxy functional group phosphorous epoxy resin with DOPO and novolac epoxy.And solidify using resol, DICY as solidifying agent, fine through modified curing system heat-proof combustion-resistant performance.Xiong Tao etc. (containing the synthesis [J] of naphthyridine ketone structure neo-epoxy resin. petrochemical complex, 2003,32 (5): 426-429) by rigid structure 4-(4-hydroxyphenyl) 2,3-naphthyridine-1-ketone is incorporated in epoxy backbone, has synthesized the epoxy resin containing naphthyridine ketone structure.
Summary of the invention
Object of the present invention aims to provide a kind of novel reaction type phosphonium flame retardant, synthetic method and application thereof, fire retardant of the present invention is P contained compound, it can be used as the fire retardant with reactivity resin (can with hydroxyl generation chemical reaction), it is by being incorporated in the molecular structure of macromolecular material by phosphoric with the form of covalent linkage, improve the flame retardant properties of these reactive resins, realize the permanent fire-retardant object of non-toxic efficient.
The invention provides a kind of phosphorous reactive flame retardant, its chemical name is that the assorted-10-phospha-10-of two 9,10-dihydro-9-oxy is oxidized phenanthryl isophthalic alcohol (diDOPO-MDCA), and structural formula is:
The present invention also provides the synthetic method of above-mentioned phosphorous reactive flame retardant, and its chemical equation is as follows:
Concrete synthesis step is as follows:
(1) under nitrogen protection, in the reaction vessel being furnished with prolong and magnetic stir bar, DOPO (assorted-10-phospha-10-of 9,10-dihydro-9-oxy is oxidized luxuriant and rich with fragrance) is added, m-terephthal aldehyde and solvent;
(2), under stirring, heating makes solvent be in reflux state, keeps this conditioned response 5 ~ 8h;
(3) be cooled to room temperature, filter, use solvent wash throw out;
(4) above-mentioned throw out is put into vacuum drying oven to vacuumize, heating pressurize 8 ~ 10h; Be cooled to room temperature and obtain white powder product diDOPO-MDCA.
In above-mentioned steps (1), step (3), solvent all selects benzene or toluene.
In above-mentioned steps (1), DOPO meets with at 1g/ml-5g/ml with the mass volume ratio of solvent with the gross weight of m-terephthal aldehyde, and the mol ratio of DOPO and m-terephthal aldehyde is 1:1 ~ 1:1.2.
In above-mentioned steps (2), heating and temperature control scope is 110 DEG C ~ 130 DEG C.
In above-mentioned steps (4), heating and temperature control scope is 60 DEG C ~ 80 DEG C.
Further, the present invention also provides above-mentioned phosphorous reactive flame retardant as the application of epoxide resin material reactive flame retardant; Phosphorous reactive flame retardant as the application of polyurethane material reactive flame retardant, and provides the application of the reactive resin fire retardant of phosphorous reactive flame retardant as reacting with hydroxyl.
Beneficial effect of the present invention is: the phosphorous reactive flame retardant diDOPO-MDCA of the present invention, can be used as the solidifying agent with reactivity resin, by the dihydroxyl active group of molecular end, react with high molecular active group, phosphoric is incorporated in macromolecular chain in macromolecular material or three-dimensional curing network structure with the form of covalent linkage, the flame retardant properties of macromolecular material can not only be made to be improved, simultaneously, phosphoric key entry truly, Polymer Systems is made to be in a kind of compatible or pressure compatible state, avoid " bloom " phenomenon occurring rubber like, greatly improve the working life of macromolecular material, thus achieve these material essence non-toxic efficients target fire-retardant for a long time.
Accompanying drawing explanation
Fig. 1 is diDOPO-MDCA's
1h nmr spectrum.
Fig. 2 is diDOPO-MDCA's
31p nmr spectrum.
Embodiment
Below by embodiment, the invention will be further described.The diDOPO-MDCA that following embodiment obtains is reactive flame retardant, the application lifted only illustrates the present invention, application can not be used for limiting the present invention, allly can include in the scope of the claims of the present invention with the reactive resin of hydroxyl generation chemical reaction in diDOPO-MDCA.
In embodiment, flame retardant properties testing method is as follows:
(1) be that the bisphenol A type epoxy resin BE188 of 182 ~ 192g/mol is dissolved in 20ml toluene by 20g epoxy equivalent (weight), add the diDOPO-MDCA of 28g, mix, toluene is drained under 40 DEG C of vacuum, then baking oven is put into, 200 DEG C of solidification 8h, then rise to 230 DEG C of after fixing 2h, finally prepare fire retarding epoxide resin.
(2) by 50g diDOPO-MDCA, 50g polyether glycol 4110,4g catalyzer (A-33, dibutyl tin laurate), 2g linking agent (PC-41), 1g whipping agent (HCFC-141b), 1.5g suds-stabilizing agent (silicone oil), 1.8g distilled water mixes under high velocity agitation as component A, then by etc. the B component [polymethylene polyisocyanates (PM-200)] of stoichiometric ratio join in raw material A component, high-speed stirring (3000r/min).Be poured into fast by compound before appearance is milky white and foam in molding jig, gained foam is slaking 48h at room temperature, finally prepares flame retarded rigid polyurethane foams plastics.
Embodiment 1
Under nitrogen protection, in the 500ml single port flask being furnished with prolong and magnetic stir bar, add 43.6gDOPO successively, 13.4g m-terephthal aldehyde and 60ml toluene.Strong stirring, is heated to 110 DEG C, makes toluene be in reflux state, keeps this condition 5h.Be cooled to room temperature, filter, collecting precipitation thing, continue to use toluene wash three times.Product is put into vacuum drying oven vacuumize, be heated to 60 DEG C, pressurize 8h; Be cooled to room temperature, obtain the diDOPO-MDCA product (productive rate 90%) of 51.3g white.
Product nuclear-magnetism measures
1h NMR (Fig. 1) and
31p NMR (Fig. 2),
1h NMR (ppm, DMSO-d
6), δ=8.29 ~ 7.03ppm (20H, Ar-H), 6.47 ~ 6.24ppm (2H ,=CH-), 5.39 ~ 5.05ppm (2H, OH);
31p NMR (ppm, DMSO-d
6), δ=31.02.
Embodiment 2
Under nitrogen protection, in the 500ml single port flask being furnished with prolong and magnetic stir bar, add 43.6gDOPO successively, 13.4g m-terephthal aldehyde and 285ml toluene.Strong stirring, is heated to 130 DEG C, makes toluene be in reflux state, keeps this condition 5h.Be cooled to room temperature, filter, collecting precipitation thing, continue to use toluene wash three times.Product is put into vacuum drying oven vacuumize, be heated to 80 DEG C, pressurize 8h; Be cooled to room temperature, obtain the diDOPO-MDCA product (productive rate 90%) of 51.3g white.
Embodiment 3
Under nitrogen protection, in the 500ml single port flask being furnished with prolong and magnetic stir bar, add 43.6gDOPO successively, 13.4g m-terephthal aldehyde and 200ml toluene.Strong stirring, is heated to 120 DEG C, makes toluene be in reflux state, keeps this condition 5h.Be cooled to room temperature, filter, collecting precipitation thing, continue to use toluene wash three times.Product is put into vacuum drying oven vacuumize, be heated to 70 DEG C, pressurize 8h; Be cooled to room temperature, obtain the diDOPO-MDCA product (productive rate 90%) of 51.3g white.
Embodiment 4 flame retardant properties is tested
(1) be that the bisphenol A type epoxy resin BE188 of 182 ~ 192g/mol is dissolved in 20ml toluene by 20g epoxy equivalent (weight), add the diDOPO-MDCA of 28g, mix, toluene is drained under 40 DEG C of vacuum, then baking oven is put into, 200 DEG C of solidification 8h, then rise to 230 DEG C of after fixing 2h, finally prepare fire retarding epoxide resin.When phosphorus content reaches 1%, oxygen index reaches 26.0.
(2) by 50g diDOPO-MDCA, 50g polyether glycol 4110,4g catalyzer (A-33, dibutyl tin laurate), 2g linking agent (PC-41), 1g whipping agent (HCFC-141b), 1.5g suds-stabilizing agent (silicone oil), 1.8g distilled water mixes under high velocity agitation as component A, then by etc. the B component [polymethylene polyisocyanates (PM-200)] of stoichiometric ratio join in raw material A component, high-speed stirring (3000r/min).Be poured into fast by compound before appearance is milky white and foam in molding jig, gained foam is slaking 48h at room temperature, finally prepares flame retarded rigid polyurethane foams plastics.When phosphorus content reaches 1%, oxygen index reaches 27.0.
Claims (9)
1. a phosphorous reactive flame retardant, is characterized in that: this fire retardant chemical name is two 9,10-dihydro-9-oxies assorted-10-phospha-10-oxidation phenanthryl isophthalic alcohol diDOPO-MDCA, and structural formula is:
2. a synthetic method for phosphorous reactive flame retardant, is characterized in that, comprises following four steps:
(1) under nitrogen protection, in the reaction vessel being furnished with prolong and magnetic stir bar, add the assorted-10-phospha-10-of 9,10-dihydro-9-oxy and be oxidized luxuriant and rich with fragrance DOPO, m-terephthal aldehyde and solvent;
(2) under agitation, heating makes solvent be in reflux state, keeps this conditioned response 5 ~ 8h;
(3) be cooled to room temperature, filter, use solvent wash throw out;
(4) above-mentioned throw out is put into vacuum drying oven to vacuumize, heating pressurize 8 ~ 10h; Afterwards, be cooled to room temperature, obtain white powder product diDOPO-MDCA; Said process chemical equation is expressed as:
3. synthetic method according to claim 2, it is characterized in that, in step (1), the total mass of DOPO and m-terephthal aldehyde and the mass volume ratio of solvent are between 1g/ml ~ 5g/ml, the mol ratio of DOPO and m-terephthal aldehyde is 1:1 ~ 1:1.2, and solvent selects benzene or toluene.
4. synthetic method according to claim 2, is characterized in that, in step (2), heating and temperature control scope is 110 DEG C ~ 130 DEG C.
5. synthetic method according to claim 2, is characterized in that, in step (3), solvent selects benzene or toluene.
6. synthetic method according to claim 2, is characterized in that, in step (4), heating and temperature control scope is 60 DEG C ~ 80 DEG C.
7. phosphorous reactive flame retardant according to claim 1 is as the application of epoxide resin material reactive flame retardant.
8. phosphorous reactive flame retardant according to claim 1 is as the application of polyurethane material reactive flame retardant.
9. phosphorous reactive flame retardant according to claim 1 is as the application of the reactive resin fire retardant that can react with hydroxyl.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496505A (en) * | 2016-10-27 | 2017-03-15 | 湖北科技学院 | A kind of phosphorus nitrogen cooperative flame retardant flexible polyurethane foam |
| CN106554483A (en) * | 2016-11-23 | 2017-04-05 | 厦门大学 | A kind of phospho hetero phenanthrene structural response type fire retardant and its application |
| CN107325128A (en) * | 2017-07-05 | 2017-11-07 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of DiDOPO classes compound |
| CN107400197A (en) * | 2017-08-04 | 2017-11-28 | 武汉工程大学 | A kind of reaction-type flame-retarding epoxy curing agent and preparation method thereof |
| CN107538584A (en) * | 2017-08-31 | 2018-01-05 | 中国林业科学研究院木材工业研究所 | A kind of synthesis of phosphonitrile class reactive flame retardant and its preparation method of fire-retardant wood-based materialses |
| CN110157041A (en) * | 2019-06-04 | 2019-08-23 | 北京理工大学 | It is a kind of containing double DOPO bases and the reactive flame retardant of nitrogen and its preparation method and application |
| CN112442212A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant and preparation method and application thereof |
| CN112442073A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant and preparation method and application thereof |
| CN112442071A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant, high-molecular flame retardant, preparation method and application |
| CN113429626A (en) * | 2021-06-24 | 2021-09-24 | 中国民用航空飞行学院 | Cross-linkable flame retardant containing bis-DOPO bis-phthalonitrile, and preparation method and application thereof |
| CN117845372A (en) * | 2023-12-01 | 2024-04-09 | 江苏佩捷纺织智能科技有限公司 | Flame-retardant polyester fabric and production process thereof |
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2015
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| LIU Y.L. ET AL: "Flame-retardant epoxy resin from o-cresol novolac epoxy cured with a phosphorus-containing aralkyl novolac", 《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》 * |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496505A (en) * | 2016-10-27 | 2017-03-15 | 湖北科技学院 | A kind of phosphorus nitrogen cooperative flame retardant flexible polyurethane foam |
| CN106554483A (en) * | 2016-11-23 | 2017-04-05 | 厦门大学 | A kind of phospho hetero phenanthrene structural response type fire retardant and its application |
| CN106554483B (en) * | 2016-11-23 | 2018-12-28 | 厦门大学 | A kind of phospho hetero phenanthrene structural response type fire retardant and its application |
| CN107325128A (en) * | 2017-07-05 | 2017-11-07 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of DiDOPO classes compound |
| CN107325128B (en) * | 2017-07-05 | 2019-04-02 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of DiDOPO class compound |
| CN107400197A (en) * | 2017-08-04 | 2017-11-28 | 武汉工程大学 | A kind of reaction-type flame-retarding epoxy curing agent and preparation method thereof |
| CN107538584A (en) * | 2017-08-31 | 2018-01-05 | 中国林业科学研究院木材工业研究所 | A kind of synthesis of phosphonitrile class reactive flame retardant and its preparation method of fire-retardant wood-based materialses |
| CN110157041B (en) * | 2019-06-04 | 2020-05-29 | 北京理工大学 | Reactive flame retardant containing double DOPO groups and nitrogen, and preparation method and application thereof |
| CN110157041A (en) * | 2019-06-04 | 2019-08-23 | 北京理工大学 | It is a kind of containing double DOPO bases and the reactive flame retardant of nitrogen and its preparation method and application |
| CN112442212A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant and preparation method and application thereof |
| CN112442073A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant and preparation method and application thereof |
| CN112442071A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant, high-molecular flame retardant, preparation method and application |
| CN112442071B (en) * | 2019-08-28 | 2023-11-07 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant, high-molecular flame retardant, preparation method and application |
| CN113429626A (en) * | 2021-06-24 | 2021-09-24 | 中国民用航空飞行学院 | Cross-linkable flame retardant containing bis-DOPO bis-phthalonitrile, and preparation method and application thereof |
| CN113429626B (en) * | 2021-06-24 | 2022-05-27 | 中国民用航空飞行学院 | Cross-linkable flame retardant containing bis-DOPO bis-phthalonitrile, and preparation method and application thereof |
| CN117845372A (en) * | 2023-12-01 | 2024-04-09 | 江苏佩捷纺织智能科技有限公司 | Flame-retardant polyester fabric and production process thereof |
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