CN104017210A - Long-chain type metal coordination intumescent flame retardant and preparation method thereof - Google Patents
Long-chain type metal coordination intumescent flame retardant and preparation method thereof Download PDFInfo
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- CN104017210A CN104017210A CN201410248023.4A CN201410248023A CN104017210A CN 104017210 A CN104017210 A CN 104017210A CN 201410248023 A CN201410248023 A CN 201410248023A CN 104017210 A CN104017210 A CN 104017210A
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- flame retardant
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Abstract
The invention discloses a long-chain type metal coordination intumescent flame retardant and a preparation method thereof. The preparation method comprises the following steps of: synthesizing a long-chain type intermediate product simultaneously containing phosphorus and nitrogen elements by using polyethyleneimine, formaldehyde and phosphorous acid as raw materials; performing coordination reaction on the long-chain type intermediate product and metal acetate to obtain the long-chain type metal coordination intumescent flame retardant. The synthesis method is simple in process, easy for reaction operation and suitable for industrial production, and has low-cost and easily-available raw materials; the flame retardant does not contain halogen and belongs to the green environment-friendly flame retardant; the structural formula is shown as the formula (I) in the specification.
Description
Technical field
The present invention relates to a kind of long chain type metal-complexing expansion type flame retardant and preparation method thereof.Be specifically related to a kind ofly be applied in flame retardant area, not halogen-containing, belong to expansion type flame retardant of environmental type and preparation method thereof.
Background technology
In recent years, become increasingly active to the research and development of fire retardant material in countries in the world, and various fire-retardant products constantly come out.The gas phase of take is fire-retardant is main halogenated flame retardant, although have good flame retardant effect, discharges poisonous, corrosive gases when burning, and the mankind and environment are existed to great hidden danger.For this reason, European Union " the scrapping electronic and electrical equipment instruction " of within 2003, promulgating (WEEE) and " about forbid objectionable impurities instruction in electronic apparatus " (RoHS) in two instructions, forbids to add harmful halogenated flame retardants such as Poly Brominated Diphenyl Ethers in electronic apparatus.Compare with halogenated flame retardant, take absorb heat fire-retardant as main mineral-type fire retardant and condensed phase fire-retardant as main expansion type flame retardant (IFR) be " green " fire retardant that current scientific circles and industry member are generally acknowledged environmental protection, but this based flame retardant often needs higher addition just can make material reach the flame retardant effect of expection, flame retarding efficiency is lower, make mechanical property and the processing characteristics of material be subject to larger destruction, simultaneously, poor heat stability, decomposition temperature are low, cause the difficulty of fire-retardant high polymer processing and recovery aspect.
Summary of the invention
Above-mentioned deficiency for prior art of the present invention, provides a kind of novel not halogen-containing, non-corrosiveness, long chain type metal-complexing expansion type flame retardant that addition is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of long chain type metal-complexing expansion type flame retardant, and the general structure of this fire retardant is as shown in the formula shown in (I):
Wherein, M is Zn
2+, Co
2+, Ni
2+, Mn
2+, Fe
2+in any one; N=10～100.
Another technical problem that the present invention will solve is to provide the preparation method of above-mentioned long chain type metal-complexing expansion type flame retardant, and concrete reaction formula is as follows:
Concrete preparation process comprises:
(1) in reaction vessel, phosphorous acid is dissolved in concentrated hydrochloric acid (massfraction surpasses 37% hydrochloric acid), then adds polymine (polymerization degree n=10～200); Heated and stirred, temperature rises to after 120 ℃ in question response container, starts to drip mass percent and be 40% formalin; After reaction 1～5h, solution is cooled to normal temperature; Then add diethanolamine that pH is adjusted to neutrality, have product and separate out, filter and collect this product, use absolute ethanol washing three times, then at 40～60 ℃ of vacuum-drying 18-30 hour, obtain the intermediate product of structure formula II;
(2) under protection of inert gas state, take dehydrated alcohol as solvent, add the intermediate product of structure formula II prepared by step (1) and metal acetate salt in reaction vessel; Stir, until completely dissolved, add sodium hydroxide to carry out the acidic by-products producing in absorption reaction process, make the temperature in reaction vessel rise to reflux state; After reaction 5～10h, filtered while hot goes out crude product, and with absolute ethanol washing three times, then at 40～60 ℃ of vacuum-drying 18-30 hour, the target product that to obtain general structure be (I) is long chain type metal-complexing expansion type flame retardant.
Described phosphorous acid and the polymine mol ratio of step of the present invention (1) is 1～2: 1; Described formaldehyde and phosphorous acid mol ratio are 1～3: 1.Adopt said ratio, can guarantee that sufficient reacting carries out to positive dirction, obtain higher productive rate.
The metal acetate salt that step of the present invention (2) is described and the intermediate product mol ratio of structure formula II are 1～2: 1; Described metal acetate salt is any in zinc acetate, Cobaltous diacetate, nickel acetate, manganese acetate, iron acetate; The sodium hydroxide that step of the present invention (2) is described and the mol ratio of metal acetate salt are 0.1～1: 1.Adopt said ratio, can guarantee that product has best flame retardant properties so that metal-complexing is reasonable, can guarantee again the raising of thermostability and carbon residue amount simultaneously.
The described rare gas element of step of the present invention (2) is any in argon gas, nitrogen.
Advantage of the present invention and beneficial effect:
1. the present invention is a kind of novel long chain type metal-complexing expansion type flame retardant, in conjunction with metal catalytic, become the fire-retardant advantage of charcoal and expansion type flame retardant, heat while reducing material combustion more efficiently discharges peak value, under lower addition, can obtain better flame retardant effect.Its concrete advantage is: than small molecules type fire retardant, have easily migration,, the shortcomings such as mechanical property that easily worsen polymeric matrix poor with polymeric matrix consistency, novel long chain type metal-complexing expansion type flame retardant involved in the present invention, can have better thermostability, resistance to water soak and matrix phase capacitive, be a kind of efficient, low cigarette, environmental protection fire retarding agent that thermostability is high.Owing to having in fire retardant backbone involved in the present invention, a plurality ofly can carry out with metallic element the group of coordination, therefore can be by controlling the content of metallic element, regulate and control thermostability and the flame retardant properties of long chain type metal-complexing expansion type flame retardant, thereby give the application flexibility that this based flame retardant adapts to differing materials.
2. preparation method's easy handling of the present invention, product postprocessing is simple, and products therefrom productive rate is high, is easy to purifying.
Accompanying drawing explanation
Fig. 1 is the structure formula I of example 1 preparation of the present invention and the infrared spectrum of structure formula II.
Fig. 2 is the example 1 structure formula I of preparation of the present invention and the solid state nmr charcoal of (II) spectrum.
Fig. 3 is the example 1 structure formula I of preparation of the present invention and the solid state nmr phosphorus of (II) spectrum.
Fig. 4 is the example 1 structure formula I of preparation of the present invention and the contrast of the hot weightless picture spectrogram of structure formula II.
Fig. 5 is the FT-IR figure of the structure formula I of example 2 of the present invention and 3 preparations.
Embodiment:
Provide example below the present invention is further described, but working of an invention mode is not limited to this.Embodiment of the present invention raw material is commercially available prod.
Embodiment 1:
In outfit magnetic stirring apparatus, temperature, take into account in the 250ml four-hole boiling flask of spherical condensation tube, add phosphorous acid 0.2mol, concentrated hydrochloric acid 100ml, the polymerization degree is 100 polymine (1mmol), stir lower reflux, get 37% formalin 32ml, in 1h, be added dropwise in flask.Then under reflux temperature, continue reaction 2h.Reaction is cooled to room temperature after finishing and spent glycol amine is neutralized to neutrality, and with absolute ethanol washing three times, filters and obtain the product that structural formula is (II), yield 95%).The compound that is (II) by structural formula is PEIP (0.53mmol), zinc acetate (0.1mol), sodium hydroxide 0.05mol, dehydrated alcohol 500ml, stir lower heating reflux reaction 7h, suction filtration with absolute ethanol washing three times, filters and obtains product that structural formula is (I) (infrared spectrum of structure formula I and structure formula II is shown in Fig. 1; Solid
13cNMR nuclear-magnetism figure is shown in Fig. 2; Solid
31pNMR nuclear-magnetism figure is shown in that Fig. 2 hot weightless picture spectrogram contrast is shown in Fig. 4).
Embodiment 2:
In being equipped with magnetic stirring apparatus, temperature and taking into account the 250ml four-hole boiling flask of spherical condensation tube, add phosphorous acid 0.2mol, concentrated hydrochloric acid 100ml, the polymerization degree is 100 polymines (1mmol), stirs lower reflux, get 37% formalin 32ml, in 1h, be added dropwise in flask.Then under reflux temperature, continue reaction 2h.Reaction is cooled to room temperature after finishing and spent glycol amine is neutralized to neutrality, and with absolute ethanol washing three times, filters and obtain the product that structural formula is (II), yield 95%.The compound that is (II) by structural formula is PEIP (0.53mmol), manganous acetate (0.1mol), sodium hydroxide 0.05mol, dehydrated alcohol 500ml, stir lower heating reflux reaction 7h, suction filtration is also used absolute ethanol washing three times, filters and obtains the product (infrared spectrum of structure formula I is shown in Fig. 5) that structural formula is (I).
Embodiment 3:
In being equipped with magnetic stirring apparatus, temperature and taking into account the 250ml four-hole boiling flask of spherical condensation tube, add phosphorous acid 0.2mol, concentrated hydrochloric acid 100ml, the polymerization degree is 100 polymines (1mmol), stirs lower reflux, get 37% formalin 32ml, in 1h, be added dropwise in flask.Then under reflux temperature, continue reaction 2h.Reaction is cooled to room temperature after finishing and spent glycol amine is neutralized to neutrality, and with absolute ethanol washing three times, filters and obtain the product that structural formula is (II), yield 95%.The compound that is (II) by structural formula is PEIP (0.53mmol), cobaltous acetate (0.1mol), sodium hydroxide 0.05mol, dehydrated alcohol 500ml, stir lower heating reflux reaction 7h, suction filtration is also used absolute ethanol washing three times, filters and obtains the product (infrared spectrum of structure formula I is shown in Fig. 5) that structural formula is (I).
Above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change that the present invention is made, be all applicable to protection scope of the present invention.
Test result:
Synthetic structure formula I shown in Fig. 1 and the infrared spectrum comparative analysis of structure formula II show: in the structure before not carrying out metallic zinc coordination (II)-and PO
3h
2the characteristic peak of functional group appears at 1170cm
-1(v (PO
2)), 1050cm
-1(v (PO
2)) and 924cm
-1(v (OH)); In structure formula I after reacting with zinc acetate-PO
3h
2the characteristic peak 924cm of functional group
-1(v (OH)) obviously diminishes, and illustrated-PO
3h
2two hydroxyls participate in the bonding with Zn.In addition, at 570cm
-1there is the peak of Zn-O in place.The intermediate product of description architecture formula II can react with zinc acetate, obtains the long chain type metal-complexing expansion type flame retardant of structure formula I.
The solid state nmr charcoal spectrum comparative analysis of synthetic structure formula I shown in Fig. 2 and structure formula II shows: because carbon in the structure formula II of synthesized is all adjacent with nitrogen element, so go out peak position mainly about 52.6ppm; After reacting with zinc acetate, the carbon in structure formula I can be subject to the impact of metallic element, goes out peak position and is offset to 51.3 left and right.The intermediate product of description architecture formula II can react with zinc acetate, obtains the long chain type metal-complexing expansion type flame retardant of structure formula I.
Fig. 3 is that the example 1 structure formula I of preparation of the present invention and the comparative analysis of the solid state nmr phosphorus of (II) spectrum show: because structure formula II and (I) all contain phosphoric, therefore all have the characteristic peak of phosphoric to occur.But with zinc acetate coordination after, in phosphorus in structure formula I spectrum except being equipped with peak appearance with the structure formula II identical bits of not carrying out metal-complexing at 7ppm place, at 18.2ppm place, there is new phosphoric peak, illustrate that metallic zinc and phosphorus hydroxyl carry out after coordination, cause phosphoric chemical environment around to change, therefore intermediate product that can description architecture formula II can react with zinc acetate, obtains the long chain type metal-complexing expansion type flame retardant of structure formula I.
Fig. 4 is that the structure formula I of example 1 preparation of the present invention and the hot weightless picture spectrogram comparative analysis of structure formula II show: structure formula II is after reacting with zinc acetate, the temperature of initial decomposition of coordination product structure formula I has improved 48 ℃ with comparing of the structure formula II before coordination, maximum heat decomposition temperature has improved 19 ℃, the carbon residue amounts of 650 ℃, improve 33%, be that structure formula I is compared with structure formula II, thermostability and carbon residue amount are all greatly improved, illustrate that metal-complexing reacts successfully, in structure formula I, the existence of metallic element is improved thermostability to phosphorus-nitrogen type organic ligand and becomes charcoal effect with high-temperature catalytic.
Fig. 5 is the infrared spectrum of the structure formula I of example 2 of the present invention and 3 preparations.In structure formula I after reacting with Cobaltous diacetate or manganese acetate-PO
3h
2the characteristic peak 924cm of functional group
-1(v (OH)) obviously diminishes, and illustrated-PO
3h
2two hydroxyls have participated in the bonding of Co or Mn.The intermediate product of description architecture formula II can react with Cobaltous diacetate or manganese acetate, obtains the long chain type metal-complexing expansion type flame retardant of structure formula I.
Claims (8)
1. a long chain type metal-complexing expansion type flame retardant, is characterized in that: the general structure of this fire retardant is as shown in the formula shown in (I):
Wherein, M is Zn
2+, Co
2+, Ni
2+, Mn
2+, Fe
2+in any one; N=10～100.
2. a preparation method for long chain type metal-complexing expansion type flame retardant claimed in claim 1, is characterized in that: the reaction formula of the method comprises:
Concrete preparation process comprises:
(1) in reaction vessel, phosphorous acid is dissolved in concentrated hydrochloric acid, then adds the polymine of polymerization degree n=10～200; Heated and stirred, temperature rises to after 120 ℃ in question response container, starts to drip mass percent and be 40% formalin; After reaction 1～5h, solution is cooled to normal temperature; Then add diethanolamine that pH is adjusted to neutrality, have product and separate out, filter and collect this product, use absolute ethanol washing three times, then at 40～60 ℃ of vacuum-drying 18-30 hour, obtain the intermediate product of structure formula II;
(2) under protection of inert gas state, take dehydrated alcohol as solvent, add the intermediate product of structure formula II prepared by step (1) and metal acetate salt in reaction vessel; Stir, until completely dissolved, add sodium hydroxide to carry out the acidic by-products producing in absorption reaction process, make the temperature in reaction vessel rise to reflux state; After reaction 5～10h, filtered while hot goes out crude product, and with absolute ethanol washing three times, then at 40～60 ℃ of vacuum-drying 18-30 hour, the target product that to obtain general structure be (I) is long chain type metal-complexing expansion type flame retardant.
3. the preparation method of long chain type metal-complexing expansion type flame retardant according to claim 2, is characterized in that: described phosphorous acid and the polymine mol ratio of step (1) is 1～2: 1.
4. the preparation method of long chain type metal-complexing expansion type flame retardant according to claim 2, is characterized in that: described formaldehyde and the phosphorous acid mol ratio of step (1) is 1～3: 1.
5. the preparation method of long chain type metal-complexing expansion type flame retardant according to claim 2, is characterized in that: the mol ratio of the metal acetate salt that step (2) is described and the intermediate product of structure formula II is 1～2: 1.
6. the preparation method of long chain type metal-complexing expansion type flame retardant according to claim 2, is characterized in that: the described metal acetate salt of step (2) is any in zinc acetate, Cobaltous diacetate, nickel acetate, manganese acetate, iron acetate.
7. the preparation method of long chain type metal-complexing expansion type flame retardant according to claim 2, is characterized in that: the described rare gas element of step (2) is any in argon gas, nitrogen.
8. the preparation method of long chain type metal-complexing expansion type flame retardant according to claim 2, is characterized in that: the sodium hydroxide that step (2) is described and the mol ratio of metal acetate salt are 0.1～1: 1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105113261A (en) * | 2015-09-18 | 2015-12-02 | 浙江理工大学 | Fabric with expansive type flame retardant coatings loaded with metal ions on surfaces and preparation method of fabric |
| CN105542159A (en) * | 2016-02-18 | 2016-05-04 | 厦门大学 | Branched chain type macromolecule phosphorus and nitrogen containing activity flame retardant and synthetic method thereof |
| CN107344998A (en) * | 2017-05-16 | 2017-11-14 | 北京工商大学 | A kind of metal complex fire retardant and preparation method thereof |
| CN108299640A (en) * | 2017-12-29 | 2018-07-20 | 广东红墙新材料股份有限公司 | A kind of application of resistance to mud collapse protection type water-reducing agent in building solid waste regenerated aggregate concrete |
| CN108794805A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | Dialkyl dithio hypophosphites, the halogen-free flame-retardant system of organic phosphite and nitrogenous compound collaboration and its application |
| CN111848681A (en) * | 2019-10-28 | 2020-10-30 | 浙江大学宁波理工学院 | Metal coordination intumescent flame retardant and preparation method thereof |
| CN115626985A (en) * | 2022-09-23 | 2023-01-20 | 浙大宁波理工学院 | Novel Mo-based polymer and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59189127A (en) * | 1983-04-11 | 1984-10-26 | Miyoshi Oil & Fat Co Ltd | Production of chelating resin |
| JPH06316811A (en) * | 1993-05-07 | 1994-11-15 | Nichibi:Kk | Method for producing chelate fiber |
| CN101163708A (en) * | 2005-01-17 | 2008-04-16 | N.V.索卢蒂亚欧洲公司 | Process for the manufacture of aminopolyalkylenephosphonic acid compounds |
| CN102153586A (en) * | 2011-01-25 | 2011-08-17 | 浙江大学宁波理工学院 | Compounds containing phosphorus, nitrogen and transition metal elements, and preparation method thereof |
| CN102391399A (en) * | 2011-10-10 | 2012-03-28 | 中国地质大学（武汉） | Preparation method for chelating ion exchange resin using inorganic substance as matrix |
| CN102448975A (en) * | 2009-05-28 | 2012-05-09 | 施里特马克控股公司 | Method for the manufacture of amino alkylene phosphonic acids |
-
2014
- 2014-06-06 CN CN201410248023.4A patent/CN104017210B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59189127A (en) * | 1983-04-11 | 1984-10-26 | Miyoshi Oil & Fat Co Ltd | Production of chelating resin |
| JPH06316811A (en) * | 1993-05-07 | 1994-11-15 | Nichibi:Kk | Method for producing chelate fiber |
| CN101163708A (en) * | 2005-01-17 | 2008-04-16 | N.V.索卢蒂亚欧洲公司 | Process for the manufacture of aminopolyalkylenephosphonic acid compounds |
| CN102448975A (en) * | 2009-05-28 | 2012-05-09 | 施里特马克控股公司 | Method for the manufacture of amino alkylene phosphonic acids |
| CN102153586A (en) * | 2011-01-25 | 2011-08-17 | 浙江大学宁波理工学院 | Compounds containing phosphorus, nitrogen and transition metal elements, and preparation method thereof |
| CN102391399A (en) * | 2011-10-10 | 2012-03-28 | 中国地质大学（武汉） | Preparation method for chelating ion exchange resin using inorganic substance as matrix |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105113261A (en) * | 2015-09-18 | 2015-12-02 | 浙江理工大学 | Fabric with expansive type flame retardant coatings loaded with metal ions on surfaces and preparation method of fabric |
| CN105542159A (en) * | 2016-02-18 | 2016-05-04 | 厦门大学 | Branched chain type macromolecule phosphorus and nitrogen containing activity flame retardant and synthetic method thereof |
| CN107344998A (en) * | 2017-05-16 | 2017-11-14 | 北京工商大学 | A kind of metal complex fire retardant and preparation method thereof |
| CN108299640A (en) * | 2017-12-29 | 2018-07-20 | 广东红墙新材料股份有限公司 | A kind of application of resistance to mud collapse protection type water-reducing agent in building solid waste regenerated aggregate concrete |
| CN108299640B (en) * | 2017-12-29 | 2020-11-10 | 上海建工建材科技集团股份有限公司 | Application of mud-resistant slump-retaining water reducer in construction solid waste recycled aggregate concrete |
| CN108794805A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | Dialkyl dithio hypophosphites, the halogen-free flame-retardant system of organic phosphite and nitrogenous compound collaboration and its application |
| CN111848681A (en) * | 2019-10-28 | 2020-10-30 | 浙江大学宁波理工学院 | Metal coordination intumescent flame retardant and preparation method thereof |
| CN111848681B (en) * | 2019-10-28 | 2023-03-28 | 浙江大学宁波理工学院 | Metal coordination intumescent flame retardant and preparation method thereof |
| CN115626985A (en) * | 2022-09-23 | 2023-01-20 | 浙大宁波理工学院 | Novel Mo-based polymer and preparation method and application thereof |
| CN115626985B (en) * | 2022-09-23 | 2023-09-05 | 浙大宁波理工学院 | Mo-based polymer and preparation method and application thereof |
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