CN102796233A - High molecular flame retarding and antistatic agent and synthetic method thereof - Google Patents
High molecular flame retarding and antistatic agent and synthetic method thereof Download PDFInfo
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- CN102796233A CN102796233A CN2012102501778A CN201210250177A CN102796233A CN 102796233 A CN102796233 A CN 102796233A CN 2012102501778 A CN2012102501778 A CN 2012102501778A CN 201210250177 A CN201210250177 A CN 201210250177A CN 102796233 A CN102796233 A CN 102796233A
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- antistatic
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Abstract
The invention discloses a synthetic method of a high molecular flame retarding and antistatic agent, and the method comprises the following step of: carrying out free radical polymerization on a flame retarding (FR) monomer, an antistatic (AS) monomer and methyl methacrylate in water under anaerobic conditions. The compound of the high molecular flame retarding and antistatic agent is a high molecular compound with a flame retarding function and an antistatic function at the same time. Low-toxic and low-smoke organophosphate plays the role of flame retarding, and a polyether high molecular permanent antistatic agent plays the role of anti-static. As the organophosphate plays the roles of both flame retarding and antistatic, the compound of the high molecular flame retarding and antistatic agent has excellent flame retarding and antistatic functions. Since the compound is a flame retarding and antistatic auxiliary agent, the compound can be fused with a high molecular material very well, has small impact on the mechanical property of the high molecular material, and is easy to form and process. After the high molecular material is added to the compound, the compound has lasting flame retarding and antistatic functions. The compound is lower in cost, easy to prepare and very suitable for industrial production.
Description
Technical field
The present invention relates to a kind of high molecular fire retardant static inhibitor and compound method.
Background technology
Because macromolecular material advantages such as especially some engineering plastics has excellent mechanical property, light weight, is easy to forming process, the weathering resistance chemical resistant properties is good, its in productive life by application more and more widely.But macromolecular material generally all has very high surface resistivity and volume specific resistance, causes electric charge to produce static in its surface accumulation easily, and then produces static hazard.Macromolecular material all is an organic polymer, removes the polymkeric substance of halogen atom-containing, and like PVC, the polymkeric substance that does not add fire retardant generally all produces fire hazard than being easier to burning.Inflammable and the easy electrostatic shortcoming that rises of macromolecular material has hindered their application in some fields.Particularly be applied in the macromolecular material of industries such as precise electronic, aviation, military project, require higher with antistatic property fire-retardant.In macromolecular material, add fire retardant and static inhibitor, can overcome the inflammable and easy electrostatic shortcoming that rises of macromolecular material.
Fire retardant be one type with physics mode or chemical mode in solid phase, liquid phase or gas phase, play a role (like heat-absorbing action, covering effect, suppress chain reaction etc.) in certain specified phase of combustion processes as heat, decomposes, ignite or the expansionary phase of flame suppresses even the interruption combustion processes, thereby give the functional aid of combustible polymers flame retardancy.Fire retardant is different by use-pattern, can be divided into additive flame retardant and reactive flame retardant.Wherein additive flame retardant is easy to use, in occupation of dominant position.Fire retardant is broadly divided into halogenated flame retardant and non-halogenated flame retardant by its chemical constitution.In the past for some time, halogenated flame retardant accounts for the overwhelming majority in fire retardant market.Because halogenated flame retardant can work in gas phase and condensed phase simultaneously; Addition seldom just can be given the material good flame-retardance; So use very extensive, but halogenated flame retardant can reduce the anti-ultraviolet stability of base material, generates more cigarette, corrosive gases and toxic gas during burning.When fire took place, these toxic gases can produce bigger harm.Switzerland research institution found halogenated flame retardant De dioxin problem in 1986, had caused people's very big concern.The environmental protection fire retarding agent of development Halogen, low cigarette, low toxicity, high heat resistance becomes the focus of scientists study.In each based flame retardant, phosphorus flame retardant, particularly organic phosphorus flame retardant mostly have advantages such as low cigarette, nontoxic, low halogen, become the focus of research.
Using static inhibitor is the main means of eliminating the macromolecular material static hazard.Static inhibitor mainly is a tensio-active agent, by the difference of method of use, can be divided into the outer spreading type static inhibitor with in add the type static inhibitor.The outer spreading type static inhibitor is a kind of temporary antistatic method, and static inhibitor is coated in polymer surface through methods such as sprayings.This static inhibitor instant effect, easy to use, but come off because of friction, washing easily.In add the type static inhibitor be before plastic shaping with its adding, mix back reshaping processing.This static inhibitor effect is lasting, is widely used, and is main static inhibitor type.The structure of pressing static inhibitor is different, can be divided into cationic static inhibitor, anionic antistatic agent, amphoteric static inhibitor, non-ionic antistatic agent and polymer permanent antistatic agent.Wherein the polymer permanent antistatic agent antistatic effect that can overcome small molecules type static inhibitor lasting with receive ambient moisture to influence big shortcoming; And heat-resisting, durable, functional strong, the development trend that suitability is wide that meet static inhibitor become the focus of people's research.
Organic phosphorus flame retardant and polymer permanent antistatic agent are respectively the focuses of fire retardant and static inhibitor research, and they are the very high using value of tool all.The compounds of this invention is a kind of polymer flame-retardant and anti-static auxiliary agent that is formed by organic phosphorous flame-retardant monomer and the antistatic monomer polymerization of polyether-type, has very wide application prospect.
Summary of the invention
The purpose of this invention is to provide a kind of high molecular fire retardant static inhibitor and compound method.
The technical scheme that the present invention taked is:
A kind of high molecular fire retardant static inhibitor is characterized in that: its structure is following:
；
Wherein, R
1Be C
6~ C
20Alkyl, X=5 ~ 20, R
2Be H or methyl; R
3Be H, CH
3, a kind of among the K, Na.
A kind of compound method of high molecular fire retardant static inhibitor may further comprise the steps: work as R
2Be H or methyl, R
3During for H or methyl, fire-retardant monomer FR, antistatic monomer A S, the material of molecular formula shown in (I) are carried out Raolical polymerizable get final product under oxygen free condition in water; Work as R
2Be H or methyl, R
3During for basic metal or alkaline earth metal ion; Fire-retardant monomer FR, antistatic monomer A S, the material of molecular formula shown in (II) are carried out Raolical polymerizable under oxygen free condition, and then the oxyhydroxide or the reactant salt of the product that obtains and basic metal or earth alkali metal got final product in water
Described fire-retardant monomer FR, antistatic monomer A S, molecular formula like (I) or the mol ratio of the material (II) be 2: (1-10): (0-10).
The temperature of reaction is 70-75 ℃.
Described oxygen free condition is the protective atmosphere environment.
The invention has the beneficial effects as follows: 1, The compounds of this invention is a kind of macromolecular compound that has anti-flaming function and anti-static function simultaneously.What play fire retardation is low toxicity, and the organophosphate of low cigarette plays the polyether type high polymer permanent anti-static agent of antistatic property.Organophosphate not only has fire retardation but also has antistatic property simultaneously, so The compounds of this invention has good flame static function.
2, because The compounds of this invention is the polymer auxiliary agent, its ability and macromolecular material well merge, and be less to the mechanical property influence of macromolecular material, and be easy to forming process.
3, The compounds of this invention has persistent fire-retardant and antistatic property after being added into macromolecular material.And the The compounds of this invention cost is lower, makes easily, very suitability for industrialized production.
Description of drawings
Fig. 1 is the infared spectrum of product A MF102.
Fig. 2 is the infared spectrum of product A MF132.
Fig. 3 is the infared spectrum of product A MF162.
Fig. 4 is the infared spectrum of product A MF182.
Fig. 5 is the infared spectrum of product A MF192.
Fig. 6 is product three's the TG collection of illustrative plates of blend, embodiment 1 preparation of the PMMA of the product that makes of the embodiment 1 of PMMA, 20wt% and 80wt%.
Embodiment
Among the present invention, the structural formula of the fire-retardant monomer FR that is mentioned is following:
The mechanism of antistatic monomer A S is illustrated as follows:
R is C
6~ C
20Alkyl, X=5 ~ 20.
The saturated straight chain alkyl that the monomeric R group of the concrete AS that uses among the following embodiment is eight carbon atoms, and X=7.
Below in conjunction with specific embodiment the present invention is done further explanation:
Embodiment 1:
At nitrogen atmosphere protection, the K of 0.49g
2S
2O
8Exist down with 150ml water, the fire-retardant monomer FR of 20mmol, the antistatic monomer A S of 10mmol, 30mmol TEB 3K (MMA) are mixed copolyreaction takes place, the temperature of copolyreaction is 70 ℃, and the time of copolyreaction is 24h.The product that obtains is designated as AMF132.
Embodiment 2:
At nitrogen atmosphere protection, the K of 0.49g
2S
2O
8Exist down with 150ml water, the fire-retardant monomer FR of 20mmol, the antistatic monomer A S of 10mmol, 60mmol TEB 3K (MMA) are mixed copolyreaction takes place, the temperature of copolyreaction is 70 ℃, and the time of copolyreaction is 24h.The product that obtains is designated as AMF162.
Embodiment 3:
At nitrogen atmosphere protection, the K of 0.49g
2S
2O
8Exist down with 150ml water, the fire-retardant monomer FR of 20mmol, the antistatic monomer A S of 10mmol, 80mmol TEB 3K (MMA) are mixed copolyreaction takes place, the temperature of copolyreaction is 70 ℃, and the time of copolyreaction is 24h.The product that obtains is designated as AMF182.
Embodiment 4:
At nitrogen atmosphere protection, the K of 0.49g
2S
2O
8Exist down with 150ml water, the fire-retardant monomer FR of 20mmol, the antistatic monomer A S of 10mmol, 90mmol TEB 3K (MMA) are mixed copolyreaction takes place, the temperature of copolyreaction is 70 ℃, and the time of copolyreaction is 24h.The product that obtains is designated as AMF192.
Embodiment 5:
At nitrogen atmosphere protection, the K of 0.49g
2S
2O
8Exist down with 150ml water, the fire-retardant monomer FR of 20mmol, the antistatic monomer A S of 10mmol are mixed copolyreaction takes place, the temperature of copolyreaction is 70 ℃, and the time of copolyreaction is 24h.The product that obtains is designated as AMF102.
In order to make the copolymer unit of product change; Can also the reaction raw materials TEB 3K among the embodiment 1-4 be changed into a kind of in methyl acrylate, methylacrylic acid, the vinylformic acid; The amount of substance of raw material keeps identical with embodiment; The condition of reaction is also identical with embodiment, can obtain the product that copolymerization units changes.
When the reaction raw materials TEB 3K among the embodiment 1-4 replaces with a kind of in methylacrylic acid, the vinylformic acid (after the replacement; The amount of each raw material remains unchanged); After obtaining product that copolymerization units changes according to same reaction conditions, can this product be immersed in also that 10-30min makes its salify in the KOH solution of NaOH solution or 10wt% of 10wt%.
Be illustrated in figure 1 as the infared spectrum of product A MF102; Fig. 2 is the infared spectrum of product A MF132.Fig. 3 is the infared spectrum of product A MF162.Fig. 4 is the infared spectrum of product A MF182.Fig. 5 is the infared spectrum of product A MF192.
Product and the blend of PMMA, the product of embodiment 1 to the embodiment 1 of PMMA, 20wt% carries out thermogravimetric analysis respectively; The TG collection of illustrative plates of gained is as shown in Figure 2; Wherein, Curve a among the figure represent PMMA (model: PMMA 14300HX), curve b represent 20wt% embodiment 1 product and 80wt% PMMA (model: blend PMMA 14300HX) (blend be prepared as common practise; Can place forcing machine to melt extrude the PMMA of the product of the embodiment 1 of 20wt% and 80wt% gets final product; Melt extruding temperature is 200-240 ℃, and screw slenderness ratio is 36:1), curve c represents the product of embodiment 1, the test condition of thermogravimetric analysis is: temperature rise rate is 8 ℃/min; Dynamic atmosphere (nitrogen), gas flow: 20ml/min.
Claims (5)
1. high molecular fire retardant static inhibitor, it is characterized in that: its structure is following:
；
Wherein, R
1Be C
6~ C
20Alkyl, X=5 ~ 20, R
2Be H or methyl; R
3Be H, CH
3, a kind of in basic metal or the alkaline earth metal ion.
2. the compound method of the described a kind of high molecular fire retardant static inhibitor of claim 1 is characterized in that: may further comprise the steps: work as R
2Be H or methyl, R
3During for H or methyl, fire-retardant monomer FR, antistatic monomer A S, the material of molecular formula shown in (I) are carried out Raolical polymerizable get final product under oxygen free condition in water; Work as R
2Be H or methyl, R
3During for basic metal or alkaline earth metal ion; Fire-retardant monomer FR, antistatic monomer A S, the material of molecular formula shown in (II) are carried out Raolical polymerizable under oxygen free condition, and then the oxyhydroxide or the reactant salt of the product that obtains and basic metal or earth alkali metal got final product in water
。
3. the compound method of a kind of flame-retardant and anti-static agent according to claim 2 is characterized in that: described fire-retardant monomer FR, antistatic monomer A S, molecular formula like (I) in the claim 2 or the mol ratio of the material (II) be 2: (1-10): (0-10).
4. the compound method of a kind of flame-retardant and anti-static agent according to claim 2 is characterized in that: the temperature of reaction is 70-75 ℃.
5. the compound method of a kind of flame-retardant and anti-static agent according to claim 2 is characterized in that: described oxygen free condition is the protective atmosphere environment.
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| CN201210250177.8A CN102796233B (en) | 2012-07-18 | 2012-07-18 | High molecular flame retarding and antistatic agent and synthetic method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778391A (en) * | 2015-12-18 | 2016-07-20 | 北京理工大学 | Flame-retardant and antistatic material for shell of handheld Raman spectrometer |
| CN108148478A (en) * | 2017-12-30 | 2018-06-12 | 上海巴德富实业有限公司 | A kind of external wall elastic lotion with antistatic effect and preparation method thereof |
| CN108864353A (en) * | 2018-06-26 | 2018-11-23 | 浙江工业大学 | A kind of antistatic PMMA composite material and preparation method of transparent flame-retarding |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341129A (en) * | 1999-02-25 | 2002-03-20 | 三菱丽阳株式会社 | Copolymer, vibration damper, vibration-damping part, and copolymer composition |
-
2012
- 2012-07-18 CN CN201210250177.8A patent/CN102796233B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341129A (en) * | 1999-02-25 | 2002-03-20 | 三菱丽阳株式会社 | Copolymer, vibration damper, vibration-damping part, and copolymer composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778391A (en) * | 2015-12-18 | 2016-07-20 | 北京理工大学 | Flame-retardant and antistatic material for shell of handheld Raman spectrometer |
| CN105778391B (en) * | 2015-12-18 | 2018-03-02 | 北京理工大学 | A kind of handheld Raman spectrometer housing flame-retardant and anti-static material |
| CN108148478A (en) * | 2017-12-30 | 2018-06-12 | 上海巴德富实业有限公司 | A kind of external wall elastic lotion with antistatic effect and preparation method thereof |
| CN108864353A (en) * | 2018-06-26 | 2018-11-23 | 浙江工业大学 | A kind of antistatic PMMA composite material and preparation method of transparent flame-retarding |
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| CN102796233B (en) | 2014-05-21 |
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