CN102585188B - Novel phosphorus-containing thermotropic liquid crystal copolyester and preparation method and application thereof - Google Patents
Novel phosphorus-containing thermotropic liquid crystal copolyester and preparation method and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 9
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- 239000003063 flame retardant Substances 0.000 claims description 20
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 19
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- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 6
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- 239000012071 phase Substances 0.000 claims description 4
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
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- Fireproofing Substances (AREA)
Abstract
Phosphorus-containing thermotropic liquid crystal copolyester is formed by polycondensation synthesis of composite binary chloride and phosphorus-containing phenols monomers in solution by using an acyl chloride method. A main chain of the phosphorus-containing thermotropic liquid crystal copolyester is provided with a mesomorphic unit, and a side chain comprises an antiflaming element phosphorus. The novel aromatic thermotropic liquid crystal copolyester does not only have excellent performance of thermotropic liquid crystals, but also has a certain antiflaming effect simultaneously. The phosphorus-containing thermotropic liquid crystal copolyester can be applied to acrylonitrile butadiene styrene (ABS) resin to prepare ABS-enhanced composite materials of phosphorus-containing thermotropic liquid crystal copolyester. The composite materials have good mechanical properties, thermal stability properties and antiflaming effects.
Description
Technical field
The invention belongs to the material modification field, be specifically related to the application of a kind of phosphorous Thermotropic Liquid, its preparation method and reinforced ABS matrix material thereof.
Background technology
Thermotropic liquid crystalline polymer (TLCP) itself has good mechanical performance and processing characteristics, big as intensity height, modulus, have self-enhancement, outstanding thermotolerance and a superior corrosion resistance etc., and can form matrix material with thermoplastic resin, give the mechanical property of matrix material excellence.In recent years, become a big focus of polymer modification about the TLCP composite study, be considered to the novel high polymer material that a class has bright prospects.
ABS resin is the multipolymer of vinyl cyanide, divinyl, three kinds of monomers of vinylbenzene, it has favorable mechanical performance, electrical insulation capability and processing characteristics, and price is relatively low, thereby is widely used in the fields such as shell, electric elements, furniture, work-at-home decoration, building and traffic of household electrical appliance and telecommunication goods.But blemish in an otherwise perfect thing is that the oxygen index of ABS resin is 18% only, burns easily in air and produces a large amount of dense smokes and toxic gas, and its amount of being fuming is maximum in various plastics.
Cause fire with meetings such as the electronics of ABS resin manufacturing, electrical accessories because of short circuit, this drawbacks limit its further application.The most frequently used way is added halogenated flame retardant exactly in ABS at present, and is both convenient economical, can obtain desirable flame retardant effect again.But along with the enhancing of people's environmental consciousness, it is imperative that halogen-free flame retardants substitutes halogenated flame retardant.Organic phosphorus flame retardant is the principal item in the halogen-free flame retardants; this based flame retardant is at when burning and polymeric matrix or its degradation production reaction generation P-O-C key; form phosphorous charing protective layer; or the netted compound that crosslinking reaction generates the how fragrant structure of Heat stability is good takes place, thereby play fire retardation.Use the phosphorous bifunctional compound of phenanthrene ring structure as the fire-resistant copolyesters monomer, this monomer is incorporated on the full aromatic(based)polymer main chain, and the O=P-O group on the molecule is positioned on the side group of polymkeric substance.When polymkeric substance was heated, the fracture of weak bond O=P-O key can not cause fracture and the degraded of main polymer chain, and therefore, this structure can not destroyed the thermostability of polymkeric substance when giving the liquid crystal polyester flame retardant resistance.People such as king's sweet smell of a specified duration in 2003 reported the research that utilizes thermotropic liquid crystal to strengthen polyethylene terephthalate (Wang Jiufen, Jiang Liping, the research of Zhou Haijun .PET/TLCP in-situ blending. plastics industry, 2003,12:16～18).This method improves the PET crystallinity by adding a spot of TLCP, and melt viscosity descends, but must add dibutyl tin laurate as catalyzer, if catalyst levels is improper, will cause the degraded of resin, have a strong impact on the performance of material, and this matrix material there is not fire-retardant effect.People such as Du Xiaohua in 2005 have reported a kind of research (Du Xiaohua of phosphorous thermotropic liquid crystal original position REINFORCED PET again, Zhao Bingshou, Yang Bing etc. phosphorous TLCP original position REINFORCED PET Mechanical Properties .2005 whole nation high molecule liquid crystal attitude and the public lecture of supramolecular ordered structure academic paper, 2005:340～344).Contain the halogen-free flameproof element phosphor among the TLCP that this author synthesizes, and TLCP is applied to the PET system.Studies show that this TLCP and PET blend can play good reinforced effects, matrix material has excellent flame-retardant performance, and addition is 3% o'clock, and limiting oxygen index(LOI) is 31.2%.But need specific reaction atmosphere in the thermotropic liquid crystal building-up process, and the matrix material that makes is used for fiber-like material more, range of application still has certain limitation.
Summary of the invention
At the problems referred to above, the invention provides a kind of thermatropic ciquid crystal with flame retardant effect and preparation method thereof, and this Thermotropic Liquid is used for the modification of ABS resin.
Phosphorous Thermotropic Liquid (hereinafter to be referred as P-TLCP) has the structure of general formula I:
Wherein the value of n is 4～8.
Above-mentioned P-TLCP adopts chloride method, and polycondensation is synthesized in solution to utilize compound binary acyl chlorides and phosphorous phenolic monomers, makes to have mesomorphic unit on its main chain, and side chain contains ignition-proof element phosphorus.This new aromatic Thermotropic Liquid not only has the performance of thermotropic liquid crystal excellence, also has certain flame retardant effect simultaneously.
Concrete building-up process is as follows:
1. the preparation of compound diprotic acid
Preparation water: under the room temperature condition, P-hydroxybenzoic acid is placed the sodium hydroxide solution of 1mol/L, be stirred to dissolving fully, as water; Wherein, the mol ratio of P-hydroxybenzoic acid and sodium hydroxide is 1: 2;
Preparation organic phase: under 60 ℃ of conditions, p-phthaloyl chloride put with tetracol phenixin mixes at 1: 12 by mass ratio, stir fully and dissolve, as organic phase;
Prepare compound diprotic acid: press mass ratio and 1: 5～6 prepare above-mentioned preparation water and organic phases, under the room temperature, organic phase is added drop-wise to aqueous phase while stirring, interface condensation reaction 4h; After reaction finished, dripping hydrochloric acid was regulated pH=3, filtered, and washing is to neutral, and drying gets white powder;
Reaction equation is as follows:
2. the preparation of compound binary acyl chlorides
Be 1 with mass ratio: the compound diprotic acid of (20～25) and thionyl chloride add in the reaction unit, add the N that is equivalent to compound diprotic acid and the two total mass 0.1% of thionyl chloride again, and dinethylformamide stirs, heating, reacts 9h under reflux temperature; Reaction steams excessive thionyl chloride after finishing under the normal pressure; Take out product, leave standstill the back and add the trichloromethane recrystallization in product, filtration, drying get white powder;
Reaction equation is as follows:
3. the preparation of phosphorous phenolic monomers
It is in 60 ℃ the reactor that DOPO and tetrahydrofuran (THF) are added design temperature, treat that DOPO dissolves fully after, coenzyme Q-10 was joined in the reactor in 30 minutes; Wherein DOPO, tetrahydrofuran (THF), coenzyme Q-10 three's mass ratio is 1: (2～2.5): 0.625; Be warming up to reflux temperature, reaction 8h takes out product, and cool to room temperature filters, and with the tetrahydrofuran (THF) washing for several times, drying gets white powder;
Reaction equation is as follows:
4. the preparation of P-TLCP
Under 100 ℃ of conditions, the phosphorous phenolic monomers that 3. step is prepared is dissolved in the orthodichlorobenzene, after being stirred to solution and being homogeneous phase, add the compound binary acyl chlorides that 2. step prepares, wherein three's mass ratio is phosphorous phenolic monomers: orthodichlorobenzene: compound binary acyl chlorides=1: (60～62): (1.14～1.16); The pyridine that evenly stirs and drip 0.5～1wt.% between the reaction period is used for the HCl gas that the absorption reaction process produces, pyridine and orthodichlorobenzene volume ratio (3.5～3.7): 100, stop to stir behind the reaction 12h, under room temperature, leave standstill 10～15h, the polymkeric substance of separating out after filtering, use methyl alcohol, tetrahydrofuran (THF), hot wash successively, drying gets powdered product and is designated as P-TLCP;
Reaction equation is as follows:
Can be observed from the structural formula of P-TLCP, the O=P-O group in its structural unit is positioned on the polymer pendant groups.When polymkeric substance was heated, the fracture of weak bond O=P-O key can not cause fracture and the degraded of main polymer chain, and therefore, this structure can not destroyed its thermostability when giving the thermotropic liquid crystal flame retardant resistance.Therefore, another object of the present invention is to the application of open P-TLCP in the ABS resin modification.
ABS resin is dry in air dry oven, P-TLCP is dry in vacuum drying oven, the above-mentioned raw materials that drying is good is by ABS: P-TLCP=100: 5 mix, in 175～185 ℃ of temperature ranges, carry out melting mixing, again through pulling-on piece, cut, and in 180 ℃ of counterdie compacting samples, obtain the ABS matrix material.
In the preferred scheme, in the mixture of ABS and P-TLCP, add two (diphenyl phosphoester) (hereinafter to be referred as the RDP) of Resorcinol, further improve the flame retardant effect of matrix material.
In the further preferred scheme, it is 100: 5: 6 by mass fraction ABS: P-TLCP: RDP.
Concrete processing parameter and the course of processing are as follows:
1, two roll temperatures and process period
Preliminary roller: roller after 180 ± 10 ℃: 170 ± 10 ℃ of refining sheet time: 10min
2, vulcanizing press compressing tablet
Top plate temperature: 180 ± 10 ℃ of lower bolster temperature: 180 ± 10 ℃
Clamp time: 420s molding pressure: 15MPa
3, raw materials pretreatment
ABS should be dried 2～4 hours in 80 ℃ of air dry ovens before use in advance;
P-TLCP should be dried 2～4 hours in 120 ℃ of vacuum drying ovens before use in advance.
4, raw material mixes
Adopt two roller mills to carry out mixing to ABS and P-TLCP and RDP.
5, the preparation of matrix material
Tablet with two roller mills are taken off overlays between two templates by same differently-oriented directivity, places in the vulcanizing press pressurize 10 minutes.Take out model, the certain hour of colding pressing is cut out sample through omnipotent sampling machine, for every performance test.
Than prior art, the present invention has following outstanding feature:
1, the thermatropic ciquid crystal copolyesters among the present invention adopts solution polycondensation to synthesize, and its advantage is to react and can carries out under low boiling point solvent and normal pressure, and particularly reaction does not need the nitrogen atmosphere protection.
2, the present invention adopts synthetic P-TLCP and the ABS blend of raw material of analytical pure level and technical grade respectively, and the performance of composites that obtains changes little (seeing Table 3).Show that this P-TLCP synthetic route is feasible, and method is simple, easy handling, has the value that industry is promoted.
3, synthetic thermatropic ciquid crystal copolyesters contains the halogen-free flameproof element phosphor among the present invention.With P-TLCP and engineering plastics ABS blend, can improve mechanical property and the thermostability of ABS, and give the certain flame retardant effect of matrix material (seeing Table 1,3).
4, after 1 basis adds an amount of RDP, can further improve the flame retardant effect (seeing Table 2) of matrix material.
Table 1
Table 2
Table 3
Description of drawings
Fig. 1 is the photo that embodiment 1 products therefrom is taken under polarizing microscope under its melting range scope.
Fig. 2 is the wide-angle x-ray diffraction spectrogram of embodiment 1 products therefrom.
Fig. 3 is that embodiment 3 gained matrix materials impact section amplifies 200 times figure under scanning electron microscope.
Fig. 4 is thermal weight loss and the weight loss rate graphic representation of embodiment 3 gained matrix materials.
Embodiment
The following examples can make those of ordinary skill in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1
Suc as formula the phosphorous Thermotropic Liquid shown in the I, its preparation method is as follows:
Take by weighing the 6.6g P-hydroxybenzoic acid and be dissolved in 100ml, in the NaOH solution of 1mol/L, place the there-necked flask of 500ml as water.Again the 4.06g p-phthaloyl chloride is dissolved in 50mlCCl
4In as organic phase.Under the room temperature organic phase is added drop-wise to the aqueous phase that has whipping appts, adds hydrochloric acid to pH=3 behind the reaction 4h, with sedimentation and filtration, with deionized water and washing with acetone several, vacuum-drying gets compound diprotic acid;
With the compound diprotic acid of 5g, the thionyl chloride of 50ml and 0.02mlN, dinethylformamide, add and be equipped with in the there-necked flask of magnetic agitation, reflux condensing tube, drying tube and device for absorbing tail gas, react 9h under reflux temperature, normal pressure steams excessive thionyl chloride, with the trichloromethane recrystallization for several times, vacuum-drying obtains compound binary acyl chlorides;
The 10ml tetrahydrofuran (THF) is placed 60 ℃ the flask that has magnetic agitation and prolong, put into 4gDOPO again, treat to add the 2.5g coenzyme Q-10 again after it fully dissolves, be warming up to reflux temperature.Stopped reaction behind the 8h takes out product, and cool to room temperature filters, and with the tetrahydrofuran (THF) washing for several times, vacuum-drying gets phosphorous phenolic monomers;
Under 100 ℃ condition, get the phosphorous phenolic monomers 4.2g that above reaction obtains and be dissolved in the 20ml orthodichlorobenzene, after being stirred to solution and being homogeneous phase, add the synthetic compound binary acyl chlorides of 4.87g.Evenly stir also between the reaction period and at the uniform velocity drip the pyridine that 0.73ml concentration is 1wt.%, stop behind the 12h stirring, under room temperature, leave standstill 10h, the polymkeric substance of separating out after filtering, use methyl alcohol, tetrahydrofuran (THF), hot wash successively, vacuum-drying gets phosphorous Thermotropic Liquid.
The raw materials used compound of present embodiment is analytical pure.
Embodiment 2
Step by embodiment 1 prepares phosphorous Thermotropic Liquid, but replaces the raw material of the analytical pure level among the embodiment 1 with industrial raw material.
Embodiment 3
ABS is placed air dry oven, and 80 ℃ following dry 2～4 hours; Embodiment 1 synthetic P-TLCP is placed vacuum drying oven, and 120 ℃ following dry 2～4 hours.ABS after the drying treatment and P-TLCP are by 100: 5 two roller mill mixings 10 minutes (forward and backward roll temperature is respectively 180 ℃, 170 ℃) of warp of mass ratio.After the mixing end, tablet is stacked in the mould, move in the vulcanizing press, mold pressing 420s under 180 ℃, 15MPa.Take out model at last, the standard batten is made in coldmoulding, carries out every performance test.
Embodiment 4
ABS is placed air dry oven, and 80 ℃ following dry 2～4 hours; Embodiment 1 synthetic P-TLCP is placed vacuum drying oven, and 120 ℃ following dry 2～4 hours.ABS after the drying treatment and P-TLCP are through two roller mill mixings (forward and backward roll temperature is respectively 180 ℃, 170 ℃), and mixing even back adds RDP, mixing 10 minutes; ABS: P-TLCP: RDP is 100: 5: 6.After the mixing end, tablet is stacked in the mould, move in the vulcanizing press, mold pressing 420s under 180 ℃, 15MPa.Take out model at last, the standard batten is made in coldmoulding, carries out every performance test.
Embodiment 5
ABS is placed air dry oven, and 80 ℃ following dry 2～4 hours; Embodiment 2 synthetic P-TLCP are placed vacuum drying oven, and 120 ℃ following dry 2～4 hours.ABS after the drying treatment and P-TLCP are by 100: 5 two roller mill mixings 10 minutes (forward and backward roll temperature is respectively 180 ℃, 170 ℃) of warp of mass ratio.After the mixing end, tablet is stacked in the mould, move in the vulcanizing press, mold pressing 420s under 180 ℃, 15MPa.Take out model at last, the standard batten is made in coldmoulding, carries out every performance test.
Embodiment 6
ABS is placed air dry oven, and 80 ℃ following dry 2～4 hours; Embodiment 2 synthetic P-TLCP are placed vacuum drying oven, and 120 ℃ following dry 2～4 hours.ABS after the drying treatment and P-TLCP are through two roller mill mixings (forward and backward roll temperature is respectively 180 ℃, 170 ℃), and mixing even back adds RDP, mixing 10 minutes; ABS: P-TLCP: RDP is 100: 5: 6.After the mixing end, tablet is stacked in the mould, move in the vulcanizing press, mold pressing 420s under 180 ℃, 15MPa.Take out model at last, the standard batten is made in coldmoulding, carries out every performance test.
Comparative Examples 1
ABS is placed air dry oven, and 80 ℃ following dry 2～4 hours.ABS after the drying treatment was through mixing 10 minutes of two roller mills (forward and backward roll temperature: 180 ℃, 170 ℃).After the mixing end, tablet is stacked in the mould, move in the vulcanizing press, mold pressing 420s under 180 ℃, 15MPa.Take out model at last, the standard batten is made in coldmoulding, carries out every performance test.
The present invention adopts the XS-18 polarizing microscope that the liquid crystal texture of copolyesters is characterized (see figure 1), and adopts wide-angle X ray diffractor that copolyesters is carried out the structural characterization (see figure 2).The present invention also adopts inside pattern and the structure of JSM-6460LV type scanning electron microscope analysis matrix material, and the sampling bar impacts section part 1～2cm, carries out the morphology analysis (see figure 3) in scanning electron microscope; Adopt Q50 type thermal gravimetric analyzer to investigate the thermal characteristics (see figure 4) of matrix material simultaneously; And by oxygen index test and vertical combustion test to matrix material, determine its flame retardant properties, the results are shown in Table 2.
Can observe from Fig. 1, this P-TLCP has thermotropic liquid crystal, and its mesomorphic phase is nematic.Show that the introducing of phosphoric does not destroy the liquid crystal state of Thermotropic Liquid.Meanwhile, in the wide-angle x-ray diffraction spectrogram as Fig. 2 P-TLCP, near 2 θ are 25 °, diffuse peaks is arranged, what this zone was corresponding is ordered structure, feature with nematic liquid crystal, thereby proved that further this P-TLCP belongs to the thermotropic liquid crystal of typical nematic, and had higher crystallinity.Tangible microfibrillar structure as can see from Figure 3 illustrate P-TLCP fibroblast well in ABS, forms the self-enhancement skeleton, makes the performance of composites raising.Fig. 4 is matrix material thermogravimetric curve figure and weight loss rate curve, matrix material is 396 ℃ in weightless 5% o'clock temperature, initial decomposition temperature is higher, system initial stage good thermal stability, the carbon residue amount is 15.2%, maximum weight loss rate is 1.28%/℃, temperature when weightless maximum rate is 458 ℃, the better heat stability of P-TLCP reinforced ABS matrix material, compare weightless 5% o'clock temperature of pure ABS and exceed 33 ℃, the carbon residue amount exceeds 13.1%, illustrates that the adding of P-TLCP can improve the thermal characteristics of ABS.
As shown in table 2, adopt synthetic P-TLCP and the ABS blend of raw material of analytical pure level to make matrix material among the present invention, its oxygen index is 22.2, has had certain flame retardant effect.Matrix material after adding RDP and P-LCP cooperating, its oxygen index can reach 26.0, compares pure ABS and has improved 8.0, and flame retardant effect is obvious.In addition, behind the P-TLCP and ABS blend that the raw material of employing technical grade synthesizes, the oxygen index of matrix material also can reach 21.0, has the effect that slows down the ABS burning.After adding RDP again, the oxygen index of this matrix material is 24.2, has had flame retardant effect.Show that the matrix material that the present invention obtains has excellent flame-retardant performance, and be expected to realize the industry popularization.
From table 3, can find, adding along with P-TLCP, the tensile strength of matrix material, breaking tenacity and Young's modulus increase, this is owing to the phenyl ring that contains in its molecular chain than multiple stiffness, easily form the rigidity uncrimping chain, and be orientated vertically, molecular packing density is big, and the modulus of matrix material and intensity are risen.In embodiment 3, the tensile strength of this matrix material, yield strength, breaking tenacity, Young's modulus exceed pure ABS 6.3MPa, 1.3MPa, 14.5MPa, 2.16GPa respectively, and particularly breaking tenacity improves significantly.Although shock strength decreases, only differ 1.5KJ/m with pure ABS
2, illustrate that the adding of P-TLCP is very little to the toughness influence of matrix material.Data from table can be found in addition, adopt the matrix material of the synthetic P-TLCP reinforced ABS of technical grade and analytical pure level raw material respectively, and the mechanical property of these two kinds of matrix materials differs very little, illustrates that the present invention has the favorable industrial promotional value.
Claims (5)
1. phosphorous Thermotropic Liquid has the structure of formula I:
Wherein the value of n is: 4～8.
2. the preparation method of the described phosphorous Thermotropic Liquid of claim 1 is synthetic with compound binary acyl chlorides and the reaction of phosphorous phenolic monomers, comprises the steps:
1. the preparation of compound diprotic acid
Preparation water: under the room temperature condition, P-hydroxybenzoic acid is placed the sodium hydroxide solution of 1mol/L, be stirred to dissolving fully, as water; Wherein, the mol ratio of P-hydroxybenzoic acid and sodium hydroxide is 1:2;
Preparation organic phase: under 60 ℃ of conditions, p-phthaloyl chloride put with tetracol phenixin mixes by mass ratio 1:12, stir fully and dissolve, as organic phase;
Prepare compound diprotic acid: press mass ratio 1:5～6 and prepare above-mentioned preparation water and organic phase, under the room temperature, organic phase is added drop-wise to aqueous phase while stirring, interface condensation reaction 4h; After reaction finished, dripping hydrochloric acid was regulated pH=3, filtered, and washing is to neutral, and drying gets white powder;
2. the preparation of compound binary acyl chlorides
Be 1:(20～25 with mass ratio) compound diprotic acid and thionyl chloride add in the reaction unit, add the N of the two quality 0.1% again, dinethylformamide stirs, heating, reacts 9h under reflux temperature; Reaction steams excessive thionyl chloride after finishing under the normal pressure; Take out product, leave standstill the back and add the trichloromethane recrystallization in product, filtration, drying get white powder;
3. the preparation of phosphorous phenolic monomers
It is in 60 ℃ the reactor that DOPO and tetrahydrofuran (THF) are added design temperature, treat that DOPO dissolves fully after, coenzyme Q-10 was joined in the reactor in 30 minutes; Wherein DOPO, tetrahydrofuran (THF), coenzyme Q-10 three's mass ratio is 1:(2～2.5): 0.625; Be warming up to reflux temperature, reaction 8h takes out product, and cool to room temperature filters, and with the tetrahydrofuran (THF) washing for several times, drying gets white powder;
4. the preparation of phosphorous Thermotropic Liquid
Under 100 ℃ of conditions, the phosphorous phenolic monomers that 3. step is prepared is dissolved in the orthodichlorobenzene, after being stirred to solution and being homogeneous phase, add the compound binary acyl chlorides that 2. step prepares, wherein three's mass ratio is phosphorous phenolic monomers: orthodichlorobenzene: compound binary acyl chlorides=1:(60～62): (1.14～1.16); The pyridine that evenly stirs and drip 0.5～1wt.% between the reaction period is used for the HCl gas that the absorption reaction process produces, pyridine and orthodichlorobenzene volume ratio (3.5～3.7): 100, stop behind the 12h stirring, under room temperature, leave standstill 10～15h, the polymkeric substance of separating out after filtering, use methyl alcohol, tetrahydrofuran (THF), hot wash successively, drying gets powdered product and is phosphorous Thermotropic Liquid.
3. the application of the described phosphorous Thermotropic Liquid of claim 1 in modified ABS resin, it is characterized in that: be that ABS resin, phosphorous Thermotropic Liquid is dry in air dry oven and vacuum drying oven respectively, the raw material that drying is good is by ABS: phosphorous Thermotropic Liquid=100:5 mixes, in 175～185 ℃ of temperature ranges, carry out melting mixing, again through pulling-on piece, cut, and in 180 ℃ of counterdie compacting samples, obtain the ABS matrix material.
4. according to the application of the described phosphorous Thermotropic Liquid of claim 3 in modified ABS resin, it is characterized in that, in the mixture of ABS and phosphorous Thermotropic Liquid, add Resorcinol two (diphenyl phosphoester), further improve the flame retardant effect of matrix material.
5. according to the application of the described phosphorous Thermotropic Liquid of claim 4 in the modified ABS resin resin, it is characterized in that, press mass fraction ABS: phosphorous Thermotropic Liquid: Resorcinol two (diphenyl phosphoester) is 100:5:6.
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