CN102070869B - Low-smoke density additive-type flame retardant resin and application thereof - Google Patents
Low-smoke density additive-type flame retardant resin and application thereof Download PDFInfo
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Abstract
The invention discloses a low-smoke density additive-type flame retardant resin which comprises 45-70 parts of unsaturated polyester resins by mass, 0.5-10 parts of mixtures of fumed silica and bentonite by mass, 4-8 parts of zinc borate by mass, 5-30 parts of aluminum hydroxide by mass and 5-30 parts of ammonium polyphosphate flame retardants by mass. The ammonium polyphosphate, the zinc borate and the aluminum hydroxide are combined and added to the unsaturated polyester resins to prepare the low-smoke density additive-type flame retardant resin which has the characteristics of low smoke density during burning, good mechanical performance and the like. Through the synergistic effect of the fumed silica and the bentonite, resin settlement can be prevented and the storage stability of the resin can be improved. The low-smoke density additive-type flame retardant resin provided by the invention is mainly applicable to the fields such as traffic vehicles, buildings, shipbuilding, chemical equipment, electronics, sports equipment, daily equipment and the like.
Description
Technical field
The present invention relates to a kind of flame-retarded resin that contains vibrin; Relating in particular to a kind of is matrix with the unsaturated polyester resin; Add the composite additive flame retardant resin that forms of multiple fire retardant, auxiliary agent and filler again, have low cigarette and non-toxic nature, be particularly useful for the glass reinforced plastic hand and stick with paste technology.
Background technology
(Unsaturated Polyester Resin is that the linear macromolecule that divalent alcohol, monounsaturated dicarboxylic acid acid anhydride or monounsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride or unsaturated dibasic acid melt phase polycondensation form is dissolved in a kind of liquid form mixt with reactive behavior that forms in the vinyl monomer UPR) to unsaturated polyester resin.Copolymerization takes place, the crosslinked cancellated solid-state material in space that forms again in this mixture under heat, light or action of evocating.The premium properties of unsaturated polyester resin makes it be widely used in fields such as vehicular traffic, building, shipbuilding, chemical plant, electronic apparatus, sports equipment and daily equipment, is the maximum matrix resin of consumption in the current composite industry.Because unsaturated polyester resin main composition element is carbon, hydrogen and oxygen element, causes it to have inflammable characteristics, and then limits its application in fields such as fire-retardant demanding rail traffic vehicles, material of construction, ship parts, electronic apparatuss.
The existing flame-retarded technology of unsaturated polyester resin divides according to the starting material of its performance anti-flaming function, can be divided into halogen-type and non-bittern type.The flame-retarded unsaturated polyester resin of halogen-type contains haloid elements such as chlorine or bromine usually, though flame retardant effect is good, incendiary toxicity and smog are very big, in case burning causes people's death by suffocation easily.Along with the progressively lifting of environmental protection, health requirements, flame-retarded unsaturated polyester resin must be to low cigarette, nontoxic trend development.
Chinese invention patent application 200510031588.8 discloses a kind of unsaturated polyester resin of heat-proof combustion-resistant, based on N-(2,4,6 tribromo phenyl) maleimide, adopts the method for melt phase polycondensation to process.C2-4 divalent alcohol, C4-10 saturated dicarboxylic acid, the synthetic unsaturated polyester ester oligomer of maleic anhydride, with vinylbenzene and reactive flame retardant N-(2,4; 6 tribromo phenyl) mixture of maleimide is made linking agent; The synthetic unsaturated polyester resin that obtains, though have flame retardant effect preferably, it is very big to produce smog in the resin combustion processes; Gas toxicity is very high, causes people's death by suffocation easily.
Chinese invention patent application 200810205303.1 discloses a kind of novel environment friendly flame-retarded unsaturated polyester resin, and it is fire-retardant unsaturated polyester and be used for the vehicles, building, electrical equipment etc. and require fire-retardant glass reinforced plastic parts that this resin can replace halogen.Resin is processed unsaturated polyester with divalent alcohol and diprotic acid or acid anhydrides condensation.Contain solid reaction type phosphorus flame retardant and liquid phosphonium flame retardant in the unsaturated polyester resin, and the content of phosphoric is not less than 4% of total mass in the resin.The response type phosphorus flame retardant has been selected hydroxy phenyl phosphinylidyne propionic acid, hydroxy phenyl phosphonoacetic acid or its combination for use; The liquid phosphonium flame retardant has been selected one or more in triethyl phosphate, triphenylphosphate, the methyl-phosphoric acid dimethyl ester for use.
Chinese invention patent application 200910156618.6 discloses a kind of flame-retardant type unsaturated polyester resin, comprises the divalent alcohol of parts by weight 17-26, the CEPPA of 12-22, the dibasic acid anhydride of 20-32, the thinner of 25-36 and the SULPHOSUCCINIC ACID ESTER melamine salt of 6-8.Add a certain amount of SULPHOSUCCINIC ACID ESTER melamine salt in the reaction later stage, can improve flame retardant properties in the CEPPA synergy.
Though it is that fire-retardant unsaturated polyester exists defective that these technology have solved halogen, the viscosity of resin is higher, and practical application receives certain restriction.
Summary of the invention
One object of the present invention is to provide a kind of low smoke density additive flame retardant resin, and effectively solving halogen is the defective that fire-retardant unsaturated polyester exists.
Another object of the present invention is to provide a kind of low smoke density unsaturated polyester resin, and it is used in the middle of low cigarette/nontoxic flame-retardant resin as matrix resin.
Low smoke density additive flame retardant resin provided by the invention comprises unsaturated polyester resin, aerosil, wilkinite, zinc borate, white lake and ammonium polyphosphate based flame retardant.
With those skilled in the art's cognitive consonance, unsaturated polyester resin is to be dissolved in a kind of liquid form mixt with reactive behavior that forms in the vinyl monomer through the linear macromolecule that divalent alcohol, monounsaturated dicarboxylic acid acid anhydride or molten monomer polycondensations such as monounsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride or unsaturated dibasic acid form.The present invention hangs down smoke density additive flame retardant resin, unsaturated polyester resin wherein, and by mass parts, consumption is 45-70 part.
Utilize aerosil and bentonitic synergy, prevent resin settled, improve the stability in storage of resin.The present invention hangs down smoke density additive flame retardant resin, and aerosil and wilkinite add with form of mixtures, and by mass parts, the total consumption of aerosil and wilkinite is 0.5-10 part.
Ammonium polyphosphate is the poly-phosphate of a kind of N of containing and P, by its polymerization degree can be divided into oligomeric, in gather and height gathers 3 kinds, its polymerization degree highly water-soluble more is more little, otherwise then water-soluble big more.Can be divided into crystallization shape and amorphous by its structure, the crystal form ammonium polyphosphate is a long-chain shape water-insoluble salt.The general molecular formula of ammonium polyphosphate is (NH4)
(n+2)P
nO
(3n+1), when n is 10-20, for water-soluble; When n greater than 20 the time, be insoluble.Ammonium polyphosphate has the expandable flame retardant function, helps falling cigarette and anti-drippage.The present invention hangs down smoke density additive flame retardant resin, the polymerization degree of used ammonium polyphosphate as: 800,1000 or 2000, median size is the 1000-5000 order, by mass parts, the ammonium polyphosphate consumption is 5-30 part.
White lake not only has fire retardation as flame-retardant additive, can also prevent to be fuming, do not produce dropping, not produce toxic gas.The present invention hangs down smoke density additive flame retardant resin, and the white lake median size is the 1500-8000 order, and by mass parts, the white lake consumption is 5-30 part.
Zinc borate is a kind of non-halogen flame retardant of environment-friendly type.The present invention hangs down smoke density additive flame retardant resin, and by mass parts, the zinc borate consumption is 4-8 part.
The present invention carries out proportioning combination with ammonium polyphosphate, zinc borate and white lake, and makes low smoke density additive flame retardant resin in the middle of making an addition to unsaturated polyester resin, characteristics such as low, the good mechanical property of smoke density when having burning.In the resin that the present invention makes, add the phosphoric acid ester fire retardant again, as: but be not limited only to, behind methyl-phosphoric acid dimethyl ester, tricresyl phosphite second fat and triphenyl phosphite a kind of or several kinds, the smoke density in the time of further reducing burning improves mechanical property.By mass parts, phosphoric acid ester fire retardant consumption is 0-10 part, and this based flame retardant consumption is preferentially selected 1-10 part.Wherein, the methyl-phosphoric acid dimethyl ester consumption is 0-4 part; Tricresyl phosphite second fat consumption is 0-4 part; The triphenyl phosphite consumption is 0-3 part.
Another kind of low smoke density additive flame retardant resin provided by the invention; By mass parts, comprise 45-70 part unsaturated polyester resin, 0.5-10 part aerosil and wilkinite mixture, 4-8 part zinc borate, 5-30 part white lake, 5-30 part ammonium polyphosphate based flame retardant and 0-10 part phosphoric acid ester fire retardant.
Various low smoke density additive flame retardant resin provided by the invention can add the filler of appropriate amount, as: by quality, use 0-10 part kaolin and 4-8 part brucite individually or simultaneously.Brucite is a kind of inorganics that has crystal water, and during burning, crystal water wherein is released out, and resin is played the coating effect, thus play fire-retardant, the cooling and control the amount of being fuming effect.
The preparation method of various low smoke density additive flame retardant resins provided by the invention; By mass parts; Under the high speed dispersor stirring condition, with 45-70 part unsaturated polyester resin, 0.5-10 part aerosil and wilkinite mixture, 5-30 part ammonium polyphosphate based flame retardant, 5-30 part white lake, and 0-10 part phosphoric acid ester fire retardant adds in the mixing vessel; Under 10-50 ℃ of temperature, mix promptly getting in 0.5-2.5 hour.
Unsaturated polyester resin of the present invention comprises a kind of unsaturated polyester, preferentially selects low viscous unsaturated polyester, and it is that a kind of weight average molecular weight is the linear polymer of 1500-3500Da.
The low viscous unsaturated polyester of the present invention comprises divalent alcohol, monounsaturated dicarboxylic acid acid anhydride or monounsaturated dicarboxylic acid and unsaturated dicarboxylic acid anhydride or unsaturated dibasic acid.
Divalent alcohol is preferentially selected carbonatoms C1-C6 divalent alcohol, as: but be not limited only to Ucar 35, terepthaloyl moietie, Diethylene Glycol, triethylene glycol, dipropylene glycol and NSC 6366 a kind of or several kinds.In unsaturated polyester of the present invention, the x of the divalent alcohol that uses is 15-20.
The monounsaturated dicarboxylic acid acid anhydride is preferentially selected Tetra hydro Phthalic anhydride.In unsaturated polyester of the present invention, the x of the dibasic acid anhydride that uses is 3-5.
Monounsaturated dicarboxylic acid is preferentially selected the diprotic acid of carbonatoms C1-C10, as: but be not limited only to m-phthalic acid, terephthalic acid, hexanodioic acid and Succinic Acid a kind of or several kinds.In unsaturated polyester of the present invention, the x of the monounsaturated dicarboxylic acid that uses is 3-5.
Unsaturated dicarboxylic acid anhydride is preferentially selected MALEIC ANHYDRIDE.In unsaturated polyester of the present invention, the x of the unsaturated dicarboxylic acid anhydride that uses is 12-15.
Unsaturated dibasic acid is preferentially selected FUMARIC ACID TECH GRADE.In unsaturated polyester of the present invention, the molecular fraction of the unsaturated dibasic acid that uses is 12-15.
A kind of unsaturated polyester provided by the invention comprises the component of following x: the C1-C6 divalent alcohol of 15-20, the Tetra hydro Phthalic anhydride of 3-5 and 12-15 MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE.
Another kind of unsaturated polyester provided by the invention comprises the component of following x: the C1-C6 divalent alcohol of 15-20, the Tetra hydro Phthalic anhydride of 3-5 and 12-15 FUMARIC ACID TECH GRADE.
Another kind of unsaturated polyester provided by the invention comprises the component of following x: the C1-C6 divalent alcohol of 15-20, the monounsaturated dicarboxylic acid of the C1-C10 of 3-5 and 12-15 MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE.
Another kind of unsaturated polyester provided by the invention comprises the component of following x: the C1-C6 divalent alcohol of 15-20, the monounsaturated dicarboxylic acid of the C1-C10 of 3-5 and 12-15 MALEIC ANHYDRIDE.
Another kind of unsaturated polyester provided by the invention comprises the component of following molecular fraction: the C1-C6 divalent alcohol of 15-20, the monounsaturated dicarboxylic acid of the C1-C10 of 3-5 and 12-15 FUMARIC ACID TECH GRADE.
Unsaturated polyester provided by the invention adds above-mentioned each component in the reaction kettle, under 190-210 ℃, makes various linear polymers through melt phase polycondensation.
Unsaturated polyester resin provided by the invention also comprises cross-linking monomer and stopper.
Cross-linking monomer is the vinyl monomer that contains unsaturated double-bond, as: but be not limited only to vinylbenzene, alpha-methyl styrene, Vinyl toluene, TEB 3K and Phthalic acid, diallyl ester a kind of or several kinds.In low viscosity unsaturated polyester resin provided by the invention, by mass parts, the consumption of cross-linking monomer is 30-50 part.
Stopper, as: but be not limited only to quinhydrones, benzoquinones, toluhydroquinone, p-ten.-butylcatechol, MEHQ a kind of or several kinds.In low viscosity unsaturated polyester resin provided by the invention, by mass parts, the consumption of stopper is 0.02-0.3 part.
Another kind of low smoke density unsaturated polyester resin provided by the invention, by mass parts, comprise following component: 45-70 part unsaturated polyester, 30-50 part are contained vinyl monomer and 0.02-0.3 part stopper of unsaturated double-bond.
Low smoke density unsaturated polyester resin provided by the invention mixes above-mentioned various unsaturated polyesters, cross-linking monomer and stopper by the relation of feeding intake under 10-60 ℃ of temperature, promptly get after cooling to room temperature.
Unsaturated polyester resin provided by the invention; Can prepare by following method: in x; Earlier with in 15-20 part divalent alcohol, 3-5 part monounsaturated dicarboxylic acid acid anhydride or monounsaturated dicarboxylic acid and 12-15 part unsaturated dicarboxylic acid anhydride or the unsaturated dibasic acid adding reaction kettle; Under 190-210 ℃ of condition, make unsaturated polyester through melt phase polycondensation; Then,,, under 10-60 ℃ of temperature, mix, cool under the room temperature condition, promptly get unsaturated polyester resin the unsaturated polyester of 45-70 part, the cross-linking monomer of 30-50 part and the stopper of 0.02-0.3 part by mass parts.
Preferential selection; Unsaturated polyester resin solids content of the present invention is 55-62wt%; Viscosity is 0.10-0.30Pas, has the advantages that heat-drawn wire can reach 90 ℃, is particularly useful for as the additive flame retardant resin that obtains low smoke density after matrix resin and other mixing of materials.
With unsaturated polyester resin of the present invention; Especially the preferential solids content of selecting is 55-62wt%; Viscosity is that low cigarette, the nontoxic additive flame retardant resin that the unsaturated polyester resin of 0.10-0.30Pas is processed as matrix resin is mainly used in fields such as vehicular traffic, building, shipbuilding, chemical plant, electronic apparatus, sports equipment and daily equipment; Also be applicable in other production technique that requires the very low glass filament reinforced plastics of resin viscosity, be particularly useful for the glass reinforced plastic hand and stick with paste technology.With unsaturated polyester resin of the present invention is matrix resin; With thorough mixing such as ammonium polyphosphate based flame retardant, white lake, zinc borate, aerosil and wilkinites; Form low cigarette, nontoxic additive flame retardant resin, viscosity is 0.30-1.0Pas, and optimum viscosity is 0.30-0.8Pas.
Term involved in the present invention is identical with notion as the one of which.
Described " carbonatoms C1-C6 " and " carbonatoms C1-C10 " refer to carbon atom number contained in compound or the monomer molecule; Because carbon atom can't exist with the fractional form; For this reason; Be appreciated that a kind of expression-form of simple breviary, as: when carbonatoms was 1,2,3,4 or 5, we were expressed as carbonatoms C1-C5 or C1-C5.
The beneficial effect that technical scheme of the present invention realizes:
Low smoke density unsaturated polyester resin provided by the invention comprises that weight average molecular weight is unsaturated polyester, cross-linking monomer and the stopper of 1500-3500Da.This unsaturated polyester resin is 55-62wt% in solids content, and viscosity is 0.10-0.30Pas, and heat-drawn wire can reach 90 ℃, is applicable to as obtaining low viscous flame-retardant resin after matrix resin and other filler, auxiliary agent or the mixing of materials.Verification experimental verification, the oxygen index of resin solidification product can be promoted to more than 30% by 19%, and vertical combustion reaches UL-94V-0 level burning grade.
The present invention makes the resin solidification product when burning, realize low cigarette and nontoxic through in unsaturated polyester resin, adding composite fire retardants such as ammonium polyphosphate based flame retardant, white lake, zinc borate and phosphoric acid ester fire retardant.The present invention is also through the anti-sedimentation agent of aerosil and wilkinite composition, realized that additive fire-retardant unsaturated paraprex has to deposit non-setting basically effect in 6 months.
With low smoke density unsaturated polyester resin provided by the invention is matrix resin; Process the additive flame retardant resin of range of viscosities at 0.30-0.80Pas; The main fields such as vehicular traffic, building, shipbuilding, chemical plant, electronic apparatus, sports equipment and daily equipment that are suitable for are particularly suited for the glass reinforced plastic hand and stick with paste technology.
Embodiment
Below describe technical scheme of the present invention in detail.The embodiment of the invention is only unrestricted in order to technical scheme of the present invention to be described; Although the present invention is specified with reference to preferred embodiment; Those of ordinary skill in the art is to be understood that; Can make amendment or be equal to replacement the technical scheme of invention, and not break away from the spirit and the scope of technical scheme of the present invention, it all should be encompassed in the claim scope of the present invention.
The used reagent of the present invention is not if clearly indicate, then all available from Sigma-aldrich (Sigma-Aldrich).
Embodiment 1
A kind of low smoke density additive flame retardant resin of present embodiment comprises 3 parts of 55 parts of unsaturated polyester resins, 0.3 part of aerosil, 1 part of wilkinite, 10 parts of ammonium polyphosphates, 20 parts in white lake, 4 parts of methyl-phosphoric acid dimethyl esters, 6 parts of zinc borates, 10 parts of kaolin, 6 parts of brucites and triethyl-phosphites.
Making method is following:
(1) 55 parts unsaturated polyester resin is added have in the container that water coolant adds cover earlier; Add 0.3 part aerosil and 1 part bentonitic mixture again; The unlatching high speed dispersor stirs; In container adds cover, lead to water coolant simultaneously, with mixing speed at 2 minutes with the interior 3000r/min that is increased to, high speed dispersion 8-10 minute;
(2) in container, once add 10 parts ammonium polyphosphate, 20 parts white lake, 4 parts methyl-phosphoric acid dimethyl ester, 6 parts zinc borate, 10 parts kaolin, 6 parts brucite and 3 parts triethyl-phosphite again; With mixing speed at 2 minutes with the interior 3000r/min that is increased to, high speed dispersion 8-10 minute;
(3) mixing speed is adjusted to 2000r/min and carries out stirring at low speed, the viscosity of resin is finely tuned with an amount of vinylbenzene.
Embodiment 2
A kind of low smoke density additive flame retardant resin of present embodiment comprises 2 parts of 55 parts of unsaturated polyester resins, 0.4 part of aerosil, 0.8 part of wilkinite, 15 parts of ammonium polyphosphates, 18 parts in white lake, 3 parts of methyl-phosphoric acid dimethyl esters, 5 parts of zinc borates, 10 parts of kaolin, 5 parts of brucites and triethyl-phosphites.
Making method is with embodiment 1.
Embodiment 3
A kind of low smoke density additive flame retardant resin of present embodiment comprises 1 part of 55 parts of unsaturated polyester resins, 0.6 part of aerosil, 0.4 part of wilkinite, 20 parts of ammonium polyphosphates, 14 parts in white lake, 2 parts of methyl-phosphoric acid dimethyl esters, 4 parts of zinc borates, 10 parts of kaolin, 4 parts of brucites and triethyl-phosphite.
Making method is with embodiment 1.
Embodiment 4
A kind of low smoke density additive flame retardant resin of present embodiment comprises 3 parts of 55 parts of unsaturated polyester resins, 0.8 part of aerosil, 0.2 part of wilkinite, 8 parts of ammonium polyphosphates, 30 parts in white lake, 4 parts of methyl-phosphoric acid dimethyl esters, 8 parts of zinc borates, 10 parts of kaolin, 8 parts of brucites and triethyl-phosphites.
Making method is with embodiment 1.
Embodiment 5
A kind of low smoke density additive flame retardant resin of present embodiment comprises 3 parts of 55 parts of unsaturated polyester resins, 0.1 part of aerosil, 1.5 parts of wilkinites, 4 parts of ammonium polyphosphates, 32 parts in white lake, 4 parts of methyl-phosphoric acid dimethyl esters, 9 parts of zinc borates, 10 parts of kaolin, 8 parts of brucites and triethyl-phosphites.
Making method is with embodiment 1.
Embodiment 6
A kind of low smoke density additive flame retardant resin of present embodiment comprises 1 part of 55 parts of unsaturated polyester resins, 1 part of aerosil, 0.1 part of wilkinite, 31 parts of ammonium polyphosphates, 4 parts in white lake, 1 part of methyl-phosphoric acid dimethyl ester, 3 parts of zinc borates, 10 parts of kaolin, 4 parts of brucites and triethyl-phosphite.
Making method is with embodiment 1.
Embodiment 7
To the foregoing description 1-4 and embodiment 5-6 (as with embodiment 1-4 Comparative Examples) the low smoke density flame-retarded unsaturated polyester resin that makes carries out chemical property test, oxygen index test, the test of thixotroping value, anti-sedimentation function test and brushing performance test respectively, the result sees table 1.
The chemical property test, promptly viscosity test is undertaken by standard GB/T 7193.1-2008.
Oxygen index test concrete grammar is following: after 100g resin adding 2g methylethyl ketone peroxide solidifying agent is stirred; Adding the different Rinmann's green promotor of 4g again stirs; Behind the ambient cure 24h, process standard-sized sample according to fire-retardant oxygen index standard GB/T2408-2008.
The measuring method of thixotroping value is following: adopt BROOKFIELD DV-I+VISCOMETER type rotational viscosimeter, under 25 ℃ ± 0.5 ℃ temperature, carry out, behind 25 ℃ of the constant temperature; Rotating cylinder (generally using the 4# rotating cylinder) is put into sample to scale, and static 5min at first tests 60r/min; Rotate and took reading static again 5min, test 6r/min in 30 seconds; Rotate and took reading replicate(determination) 2 times in 30 seconds.The viscosity that then 6r/min surveyed and the ratio of 60r/min viscosity number are thixotropy index.
The testing method of anti-sedimentation function is following: at room temperature carry out; Usefulness is dry, 100 milliliters of clean grounds keep sample, and bottle takes by weighing 100 ± 0.1g resin sample; Flap is tight; Static being placed under the dry lucifuge environment, per Solid-Liquid Separation situation of watching resin surface in 10 days measures the height of top layer liquid with graduated scale.Separate out when no top layer liquid, give " outstanding " and estimate, the top layer liquid height was estimated less than 1cm give " better ", and the top layer liquid height gives " relatively poor " evaluation greater than 1cm's.
The testing method of brushing performance is following: under 25 ℃ ± 0.5 ℃ temperature, carry out; Evenly smear demoulding wax with 2 cun hairbrush one time No. 8 at 500 * 500mm drying, cleaning and smooth glass surface, with the clean cotton gauze demoulding wax wiped clean that glass surface is unnecessary.Get 100 ± 0.1g resin, add the cyclohexanone peroxide of 4 ± 0.1mL and the cobalt iso-octoate styrene solution (4% concentration) of 2 ± 0.1mL, dip in the resin for preparing with hairbrush and evenly brush, see surperficial brush mark thickness behind the resin solidification at glass surface.
Observe to solidify back product surface brush mark what and measure the thickness of brush mark, brush mark more less, the more uniform resin of brush mark thickness, leveling characteristics is good more, brushes more easily; Otherwise, be not easy brushing.The thickness of brush mark gives " outstanding " and estimates in the 0.7mm-0.85mm scope; " well " of thickness in the 0.85mm-1.0mm scope estimated, and thickness is estimated greater than 1cm give " relatively poor ".
From table 1, can find out; Embodiment 1-4 cured product oxygen index all surpasses 30%; This explanation greatly improves through the composite flame retardant properties of unsaturated polyester that makes of aerosil, wilkinite, ammonium polyphosphate, white lake, methyl-phosphoric acid dimethyl ester and triethyl phosphate, and smoke density is all lower, placement rear defence sedimentation function is good.
The oxygen index of embodiment 5 is lower, and placement postprecipitation effect is relatively poor; The brushing poor-performing of embodiment 6, smoke density is also higher.Therefore, embodiment 5 and 6 performance all can not satisfy request for utilization.And according to the low smoke density additive flame retardant resin of each embodiment 1-4 formulated, modest viscosity, anti-sedimentation function is excellent, oxygen index is high, the brushing performance is good, smoke density is low, can be good at satisfying the needs of moulding process.
Table 1
Claims (9)
1. one kind low smoke density additive flame retardant resin by mass parts, comprises 45-70 part unsaturated polyester resin, 0.5-10 part aerosil and wilkinite mixture, 4-8 part zinc borate, 5-30 part white lake and 5-30 part ammonium polyphosphate based flame retardant;
Said unsaturated polyester resin by mass parts, comprises following component: 45-70 part unsaturated polyester, 30-50 part are contained vinyl monomer and 0.02-0.3 part stopper of unsaturated double-bond; Said unsaturated polyester comprises that x is that divalent alcohol, the x of 15-20 carbonatoms C1-C6 is that monounsaturated dicarboxylic acid and the molecular fraction of 3-5 Tetra hydro Phthalic anhydride or carbonatoms C1-C10 is 12-15 MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE.
2. low smoke density additive flame retardant resin according to claim 1; It is characterized in that also comprising 0-10 part phosphoric acid ester fire retardant, described phosphoric acid ester fire retardant is selected from a kind of of methyl-phosphoric acid dimethyl ester, tricresyl phosphite second fat and triphenyl phosphite or several kinds.
3. low smoke density additive flame retardant resin according to claim 1 is characterized in that also comprising 0-4 part methyl-phosphoric acid dimethyl ester and 0-4 part tricresyl phosphite second fat.
4. low smoke density additive flame retardant resin according to claim 1 is characterized in that also comprising 0-10 part kaolin, 4-8 part brucite or its combination.
5. low smoke density additive flame retardant resin according to claim 1; It is characterized in that said unsaturated polyester resin solids content is 55-62wt%; Viscosity is 0.10-0.30Pas, and said unsaturated polyester resin contains the unsaturated polyester of weight average molecular weight 1500-3500Da.
6. low smoke density additive flame retardant resin according to claim 1 is characterized in that the said vinyl monomer that contains unsaturated double-bond is selected from a kind of of vinylbenzene, alpha-methyl styrene, Vinyl toluene, TEB 3K and Phthalic acid, diallyl ester or several kinds.
7. according to claim 1 or 6 described low smoke density additive flame retardant resins, it is characterized in that said divalent alcohol is selected from a kind of of Ucar 35, terepthaloyl moietie, Diethylene Glycol, triethylene glycol, dipropylene glycol and NSC 6366 or several kinds.
8. according to claim 1 or 6 described low smoke density additive flame retardant resins, it is characterized in that said diprotic acid is selected from a kind of of m-phthalic acid, terephthalic acid, hexanodioic acid and Succinic Acid or several kinds.
9. low smoke density additive flame retardant resin according to claim 1 is used for the production technique of vehicular traffic, building, shipbuilding, chemical plant, electronic apparatus, sports equipment and daily equipment and glass filament reinforced plastics.
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| JPH05271464A (en) * | 1992-03-24 | 1993-10-19 | Furukawa Electric Co Ltd:The | Fire-resistant putty composition |
| CN101343407B (en) * | 2008-08-22 | 2011-04-27 | 常熟东南塑料有限公司 | Halogen-free flame-proof unsaturated polyester molding compound |
| CN101696331B (en) * | 2009-10-30 | 2011-07-27 | 株洲市华晟实业有限公司 | Flame-retarding lacquer putty and preparation method thereof |
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