CN103073751A - Expansive type fire retardant, flame retardation polymer composition containing fire retardant and fiber enhanced polymer-based flame retardation composite material - Google Patents
Expansive type fire retardant, flame retardation polymer composition containing fire retardant and fiber enhanced polymer-based flame retardation composite material Download PDFInfo
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- CN103073751A CN103073751A CN201210483662XA CN201210483662A CN103073751A CN 103073751 A CN103073751 A CN 103073751A CN 201210483662X A CN201210483662X A CN 201210483662XA CN 201210483662 A CN201210483662 A CN 201210483662A CN 103073751 A CN103073751 A CN 103073751A
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Abstract
本发明涉及一种膨胀型阻燃剂、含有该阻燃剂的阻燃聚合物组合物，以及利用该阻燃聚合物组合物制得的纤维增强聚合物基阻燃复合材料。该膨胀型阻燃剂包含：碳源；酸源；气源；以及抗氧剂，其包括双（十八烷基）季戊四醇二亚磷酸酯及/或十六烷基季戊四醇二亚磷酸酯。复合材料包括阻燃聚合物材料本体以及位于所述本体中的连续纤维，所述阻燃聚合物材料本体与连续纤维是一体化的，所述阻燃聚合物材料本体是通过使含有该阻燃剂的阻燃聚合物组合物固化而得到，本发明制备出的纤维增强聚合物基阻燃复合材料在被火烧后，仍具备优良的热力学性能。
The invention relates to an intumescent flame retardant, a flame retardant polymer composition containing the flame retardant, and a fiber-reinforced polymer base flame retardant composite material prepared by using the flame retardant polymer composition. The intumescent flame retardant comprises: a carbon source; an acid source; a gas source; and an antioxidant including bis(octadecyl)pentaerythritol diphosphite and/or hexadecyl pentaerythritol diphosphite. The composite material includes a flame-retardant polymer material body and continuous fibers located in the body, the flame-retardant polymer material body and the continuous fiber are integrated, and the flame-retardant polymer material body is made by containing the flame-retardant It is obtained by curing the flame-retardant polymer composition of the agent, and the fiber-reinforced polymer-based flame-retardant composite material prepared by the present invention still has excellent thermodynamic properties after being burned.
Description
Technical field
The invention belongs to expansion type flame retardant and fiber reinforced polymer matrix composite field, the continuous fibre that is specifically related to a kind of quaternary expansion type flame retardant, contains the flame retardant compositions of this fire retardant and utilizes said composition to make strengthens polymer-base flame-proof composite material.
Background technology
Fiber reinforced polymer matrix composite at low temperatures (when temperature is lower than 100 ° of C) is widely used in fields such as aerospace, national defence, boats and ships and traffic because its specific tenacity is high, specific modulus is high, designability is strong, fatigue resistance is good and be convenient to the advantage such as big area global formation.Second-order transition temperature is softening, melting because the body material-polymer of polymer matrix composite is in the situation that temperature is higher than, in the situation that temperature is higher than the depolymerization of 300 ° of C molecular chains and thermolysis, after the fire, the body material of polymer matrix composite becomes residue, matrix loses the ability that binding fiber strengthens body, and the supporting capacity of structure is seriously undermined.Simultaneously, easily produce thick smoke and toxic gas in high temperature flaming combustion process, be unfavorable for people's escape, it is restricted in the application aspect the Structural Engineering of fire-prone.
The method of improving the fire resistance of polymer matrix composite comprises structure fire and material fire prevention.Aspect structure fire, can be at therebetween one deck lagging material of two-layer composite structure to reach the purpose of anti-fire.Aspect the material fire prevention, a kind of feasible method is to introduce fire-retardant group by chemical reaction in macromolecular material, thus improve material non-flame properties, stop material to be ignited and suppress flame transmission, this reactive flame retardant accounts for 15% of fire retardant.Common fire retardant is additive flame retardant, accounts for 85% of fire retardant, namely adds fire retardant in the macromolecule matrix of matrix material.Fire retardant is brought into play its fire retardation jointly by a certain or some mechanism; as suppressing the approach such as chain reaction by absorption heat, generation high-density incombustible gas dilution oxygen or inflammable gas, formation non-combustible protective membrane, the thermostability that improves polymkeric substance, Mulberry Extract; effectively stop, delay or stop flame transmission, improve the thermal characteristics of polymer matrix composite in the baked wheaten cake situation.
In order to make polymer matrix composite reach preferably fire performance, usually needing the content of the flame-retardant additive of adding is the 5-40% of polymeric matrix weight fraction, and this will reduce the thermomechanical property of polymer matrix composite.(CN 102532693A in published patent; CN 102532681A; CN 102295792A), a large amount of interpolations of fire retardant can cause the mechanical property reduction by a relatively large margin of matrix material, and are fewer to the report of the good flame-proof composite material of thermomechanical property.
Therefore, solve because fire retardant adds the problem that the thermomechanical property that causes polymer matrix composite reduces, and to prepare the good environmental protection polymer base fire-resistant composite material of thermomechanical property be one of problem that enjoys at present challenge.Carry out above-mentioned research to prevention and reduce in use contingent fire of polymer matrix composite structure, increase personnel escape's time, the life and property loss that the reduction fire causes etc. has important value.
Summary of the invention
The purpose of this invention is to provide the fiber reinforced polymer matrix composite that possesses good thermomechanical property, so first aspect present invention provides first a kind of expansion type flame retardant, it comprises:
Carbon source is for having the organic compound of a plurality of hydroxyls;
Acid source can original position generate sour compound during for mineral acid or burning;
Source of the gas can generate the nitrogenous compound of nitrogen for when burning; And
Oxidation inhibitor comprises two (octadecyl) pentaerythritol diphosphites (distearyl pentaerythritol disphosphite) and/or hexadecyl pentaerythritol diphosphites (cetyl pentaerythritol dipho sphite).
In the present invention, term " carbon source " claims again char-forming agent, is to form the foam charring layer when burning.In another preference, the organic compound with a plurality of hydroxyls comprises one or two or more kinds in cellulosic fibre (cellulose fibre), glucose, starch, sucrose, dextrin, tetramethylolmethane (pentaerythritol), ethylene glycol, the resol.
In the present invention, term " acid source " claims again dewatering agent or charing promotor.In another preference, the compound of energy original position generation acid comprises one or two or more kinds in poly-silicic acid (polysilicic acid), phosphoric acid, boric acid, sulfuric acid, phosphoric acid ester, the ammonium phosphate (ammonium phosphate) when mineral acid or burning.
In the present invention, term " source of the gas " is also named the foaming source.In another preference, nitrogenous compound comprises one or two or more kinds in urea (urea), trimeric cyanamide (melamine), the polymeric amide (polyamide).
In the present invention, term " oxidation inhibitor " is for blocking, suppress or delay polymkeric substance oxidation or autoxidation process, comprising free radical inhibitors (free radical scavenger) or peroxide decomposer.
In another preference, described oxidation inhibitor is two (octadecyl) pentaerythritol diphosphites.
In another preference, in the described fire retardant, by weight, the two ratio of the content summation of described carbon source and acid source and the content summation of source of the gas and oxidation inhibitor is 1:3 to 3:1.
In another preference, described carbon source is 2:8 to 8:2 with the content ratio of acid source.
In another preference, described source of the gas is 1:2 to 2:1 with the content ratio of oxidation inhibitor.
Second aspect present invention provides a kind of flame retardant compositions, and it comprises:
Such as aforementioned fire retardant of the present invention; And
After being heated curing, can form the polymer precursor of polymer materials.
In the present invention, term " composition " is to contain that each composition has mixed and unmixed two kinds of forms.
In another preference, described polymer precursor comprises the Resins, epoxy that contains BDDE and the stiffening agent of cycloaliphatic amines modification.
In another preference, described polymer materials comprises one or two or more kinds in Resins, epoxy, nylon, polyolefine, the polycarbonate.
Third aspect present invention provides a kind of fiber-reinforced polymer-matrix flame-proof composite material, it is characterized in that, described matrix material comprises flame-proofed polymer material body and the continuous fibre that is arranged in described body, described flame-proofed polymer material body and continuous fibre are integrated, and described flame-proofed polymer material body is to obtain by making such as aforementioned flame retardant compositions curing of the present invention.
In another preference, described matrix material has following thermomechanical property: matrix material is passing through 25kW/m
2Again according to ASTM7264-07 testing method test, the initial stiffness of the matrix material after radiation is 0.205 to 0.225KN/mm after 540 seconds in the thermal radiation flux radiation, and three-point bending strength is 370 to 403MPa.
In the present invention, term " continuous fibre " refers to continuous unremitting fiber.
In another preference, described continuous fibre is selected from one or two or more kinds in glass fibre, carbon fiber, the aramid fiber.
In another preference, described continuous fibre is form of fabric.
In another preference, with total restatement of described matrix material, the content summation of described carbon source and acid source is the 2.5wt% to 7.5wt% that accounts for matrix material.
In another preference, with total restatement of described matrix material, the content summation of described source of the gas and oxidation inhibitor is the 2.5wt% to 7.5wt% that accounts for matrix material.
In another preference, with total restatement of described matrix material, the content of described continuous fibre accounts for the 40wt% to 60wt% of matrix material.
In another preference, with total restatement of described matrix material, the content of described polymer materials body is the 35wt% to 45wt% that accounts for matrix material.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can making up mutually between specifically described each technical characterictic in below (eg embodiment), thus consist of new or preferred technical scheme.As space is limited, this tired stating no longer one by one.
Description of drawings
Fig. 1 is the quality loss curve that the explanation embodiment of the invention 1 and Comparative Examples 3 obtain by thermogravimetic analysis (TGA);
Fig. 2 is the photo of composite panel after the thermal radiation experiment that explanation embodiment 1 makes;
Fig. 3 is the photo of composite panel after the thermal radiation experiment that explanation Comparative Examples 3 makes.
Embodiment
The inventor finds through extensive and deep research, adopt the prepared fiber reinforced polymer matrix composite goods of fire retardant (this paper is hereinafter referred to as the quaternary fire retardant) that comprise simultaneously carbon source, acid source, source of the gas and oxidation inhibitor to have good thermomechanical property, can keep required rigidity and intensity after particularly burning, further, if in specified range, this matrix material will have excellent thermomechanical property with [the content summation of carbon source and acid source] and [the content summation of source of the gas and oxidation inhibitor] the two ratio control.Finished on this basis the present invention.
Expansion type flame retardant and preparation thereof
Expansion type flame retardant of the present invention comprises:
Carbon source is for having the organic compound of a plurality of hydroxyls;
Acid source can original position generate sour compound during for mineral acid or burning;
Source of the gas can generate the nitrogenous compound of nitrogen for when burning; And
Oxidation inhibitor comprises two (octadecyl) pentaerythritol diphosphites and/or hexadecyl pentaerythritol diphosphites.
Preferably, the organic compound that has a plurality of hydroxyls comprises one or two or more kinds in cellulosic fibre, glucose, starch, sucrose, dextrin, tetramethylolmethane, ethylene glycol, the resol.
Preferably, the compound that can original position generates acid comprises in poly-silicic acid, phosphoric acid, boric acid, sulfuric acid, phosphoric acid ester, the ammonium phosphate one or two or more kinds mineral acid or when burning.
Preferably, nitrogenous compound comprises one or two or more kinds in urea, trimeric cyanamide, the polymeric amide.
Preferably, oxidation inhibitor is two (octadecyl) pentaerythritol diphosphites.
Preferably, in the described fire retardant, by weight, the two ratio of the content summation of described carbon source and acid source and the content summation of source of the gas and oxidation inhibitor is 1:3 to 3:1.
Preferably, carbon source is 2:8 to 8:2 with the content ratio of acid source.
Preferably, source of the gas is 1:2 to 2:1 with the content ratio of oxidation inhibitor.
About the preparation of expansion type flame retardant of the present invention, can by known methods, for example simply four kinds of compositions be mixed to reach.Or by first carbon source and acid source being mixed into a composition (for example commercially available VISIL) and source of the gas and oxidation inhibitor are mixed into first a composition, again two compositions are mixed to prepare afterwards.
Flame retardant compositions and preparation thereof
Flame retardant compositions of the present invention comprises:
Such as aforementioned fire retardant of the present invention; And
After being heated curing, can form the polymer precursor of polymer materials.
Preferably, polymer precursor comprises the Resins, epoxy that contains BDDE and the stiffening agent of cycloaliphatic amines modification.
Preferably, polymer materials comprises one or two or more kinds in Resins, epoxy, nylon, polyolefine, the polycarbonate.
About the preparation of flame retardant compositions of the present invention, can by known methods, for example simply polymer precursor and expansion type flame retardant at room temperature be mixed to reach by mechanical stirring.
Fiber-reinforced polymer-matrix flame-proof composite material and preparation thereof
Fiber-reinforced polymer-matrix flame-proof composite material of the present invention comprises:
The flame-proofed polymer material body; And
Be arranged in the continuous fibre of described body, described flame-proofed polymer material body and continuous fibre are integrated, and described flame-proofed polymer material body is to obtain by making such as aforementioned flame retardant compositions curing of the present invention.
In another preference, described matrix material has following thermomechanical property: matrix material is passing through 25kW/m
2Again according to ASTM7264-07 testing method test, the initial stiffness of the matrix material after radiation is 0.205 to 0.225KN/mm after 540 seconds in the thermal radiation flux radiation, and three-point bending strength is 370 to 403MPa.
In the present invention, term " continuous fibre " refers to continuous unremitting fiber.
Preferably, continuous fibre is selected from one or two or more kinds in glass fibre, carbon fiber, the aramid fiber.
Preferably, continuous fibre is form of fabric.
Preferably, with total restatement of described matrix material, the content summation of described carbon source and acid source is the 2.5wt% to 7.5wt% that accounts for matrix material.
Preferably, with total restatement of described matrix material, the content summation of described source of the gas and oxidation inhibitor is the 2.5wt% to 7.5wt% that accounts for matrix material.
Preferably, with total restatement of described matrix material, the content of described continuous fibre accounts for the 40wt% to 60wt% of matrix material.
Preferably, with total restatement of described matrix material, the content of described polymer materials body is the 35wt% to 45wt% that accounts for matrix material.
About the preparation of fiber-reinforced polymer-matrix flame-proof composite material of the present invention, can adopt conventional resin transfer molding (RTM) technique to carry out.A kind of representational technique comprises step: mould cleans → is coated with preform → matched moulds that hole sealing agent → coating release agent → dress sealing-ring → pack into comprises continuous fibre, fastening → as to connect vacuum-pumping pipeline and injecting glue pipeline → vacuumize leak detection → mould, the preheating of storage glue tank → join glue (configuring flame retardant compositions of the present invention) → deaeration → pressurization → with glue (flame retardant compositions) injection mould → curing → cooling → form removal → deburring in mould.
Preferably, expansion type flame retardant of the present invention and flame-proof composite material all do not contain the halogen family element, can not discharge the toxic gases such as carbon monoxide during thermal degradation, can not discharge the corrosive gasess such as hydrogen halide yet, and be pollution-free, can not cause harm to the people.
Main beneficial effect of the present invention comprises: the fiber-reinforced polymer-matrix flame-proof composite material of preparing possesses excellent thermomechanical property, therefore this material is still possessed good rigidity and flexural strength after burning, matrix material of the present invention can be applied in fire resistance and requires high and need bear in the field of larger load.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.
＜material source 〉
1. plain weave E glass fibre: available from Britain Glasplies company, specification is 300g/m
2
2. the low-viscosity epoxy resin that contains BDDE: available from Huntsman company, model LY5052.
3. the stiffening agent of cycloaliphatic amines modification: available from Huntsman company, model HY5052.
4. the mixture that gathers silicic acid (acid source) and cellulosic fibre (carbon source): available from Finland Sateri Fibres company, product are called VISIL, and cellulosic fibre (carbon source) is 7:3 with the weight ratio of poly-silicic acid (acid source).
5. trimeric cyanamide: available from Aladdin reagent (Shanghai) Co., Ltd..
6. two (octadecyl) pentaerythritol diphosphites: available from Aladdin reagent (Shanghai) Co., Ltd., product are called antioxidant 618.
Embodiment 1:
(I) preparation of flame retardant compositions:
With 1200g Resins, epoxy LY5052 (containing stiffening agent HY5052), 75gVISIL and 75g trimeric cyanamide and 150g antioxidant 618, at room temperature mixed by mechanical stirring, and made the flame retardant compositions of the present embodiment.
(II) preparation of flame-proof composite material plate:
With 8 layers of plain weave E glass fibre (altogether 1500g) along same direction lay in the RTM mould, after mould vacuumizes, the flame retardant compositions that under a barometric point (I) is made is injected in the mould, composition was solidified 8 hours under 80 ° of C and obtain the composite panel of the present embodiment, this matrix material comprises the Visil of the continuous glass fibre of 50wt%, the Resins, epoxy of 40wt% (content that comprises the HY5052 stiffening agent), 2.5wt%, the trimeric cyanamide of 7.5wt% and antioxidant 618, as shown in table 1.
With with the similar method preparation of embodiment 1, embodiment 2,3 are in, the consumption difference of each component different with embodiment 1, as shown in table 1.
Comparative Examples 1:
With with the similar method preparation of embodiment 1, this Comparative Examples and embodiment 1 be different be in, it is different with the consumption of antioxidant 618 and other each components that flame retardant compositions does not contain trimeric cyanamide, as shown in table 1.
Comparative Examples 2:
With with the similar method preparation of embodiment 1, this Comparative Examples and embodiment 1 be different be in, flame retardant compositions does not contain the consumption difference of VISIL and other each components, and is as shown in table 1.
Comparative Examples 3:
With with the similar method preparation of embodiment 1, this Comparative Examples and embodiment 1 be different be in, flame retardant compositions does not contain VISIL, do not contain trimeric cyanamide and antioxidant 618 yet, only contains Resins, epoxy and stiffening agent, and is as shown in table 1.
Table 1
The thermomechanical property test:
(I) thermogravimetic analysis (TGA):
With thermal gravimetric analyzer (Sweden plum Teller TGA/DSC analyser) matrix material that embodiment 1 and Comparative Examples 3 obtain is carried out thermogravimetic analysis (TGA), the temperature variant quality loss curve of this two matrix material as shown in Figure 1, among Fig. 11 represents the matrix material of embodiment 1, and 2 represent the matrix material of Comparative Examples 3.Temperature rise rate is 10 ° of C/min in the test process, and air flow amount is 100 ± 5mL/min.
As seen from Figure 1, the quality loss of two matrix materials is larger between 350 to 425 ° of C, and after temperature reached 575 ° of C, the residual mass of the matrix material of Comparative Examples 3 was 50%, namely is higher than this temperature, and polymer body burns totally, only remaining glass fibre.Temperature is higher than 350 ° of C, the flame-proof composite material of embodiment 1 is less than the quality loss of Comparative Examples 3, the quaternary fire retardant that above explanation the present invention comprises carbon source, acid source, source of the gas and oxidation inhibitor simultaneously can improve the carbon yield of matrix material, also has better residual mechanical properties because flame-proof composite material remains more carbon yield after baked wheaten cake.
(II) initial stiffness and three-point bending strength test:
Such as Fig. 2 and ground illustrated in Figure 3, heat insulation processing is carried out in the non thermal radiation zone of the composite panel that each embodiment and Comparative Examples is made with ceramic coverture, the thermal radiation zone is the border circular areas (the central circular black region of Fig. 2 and Fig. 3) of diameter 50mm, and its center of circle is 60mm to the distance of free edge.In the taper calorimeter to the border circular areas of composite panel with 25kW/m
2Thermal radiation flux carried out radiation 540 seconds.Behind the composite panel cool to room temperature after the localized heat radiation, measure the load-deflection curve of composite panel under the three-point bending load by material universal testing machine Instron 3369, semisphere pressure head by diameter 15mm loads composite panel with the speed of per minute 1mm, load(ing) point obtains load-deflection curve apart from free edge 15mm.Initial stiffness value and the three-point bending strength value of the composite panel load-deflection curve after finishing thermal radiation are listed in table 2.
Table 2
Can find out from above test result, under identical test condition, the present invention comprises the adding of the quaternary fire retardant of carbon source, acid source, source of the gas and oxidation inhibitor simultaneously, make the temperature rise rate of matrix material slack-off slack-off with thermal conduction rate, therefore can obviously prolong the open-assembly time of matrix material in thermal radiation, delay the decomposition of polymkeric substance in the matrix material, improve the Rigidity and strength of matrix material after baked wheaten cake.
In sum, the present invention comprises the quaternary fire retardant of carbon source, acid source, source of the gas and oxidation inhibitor simultaneously when being used to make the fiber-reinforced polymer-matrix flame-proof composite material, can obviously prolong the open-assembly time of matrix material in thermal radiation, delay the decomposition of polymkeric substance in the matrix material, improve the Rigidity and strength of matrix material after baked wheaten cake, so fiber-reinforced polymer-matrix flame-proof composite material of the present invention, after baked wheaten cake, remain more carbon yield and have better residual mechanical properties, have better thermomechanical property than the matrix material of prior art.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (15)
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