CN101585912B - Thermotropic liquid crystal random copolyester containing phosphor and kinking groups and preparation thereof - Google Patents
Thermotropic liquid crystal random copolyester containing phosphor and kinking groups and preparation thereof Download PDFInfo
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- CN101585912B CN101585912B CN2009100599553A CN200910059955A CN101585912B CN 101585912 B CN101585912 B CN 101585912B CN 2009100599553 A CN2009100599553 A CN 2009100599553A CN 200910059955 A CN200910059955 A CN 200910059955A CN 101585912 B CN101585912 B CN 101585912B
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Abstract
The present invention discloses a thermotropic liquid crystal random copolyester containing phosphor and kinking groups, which is composed of the following structural units, wherein the structural units (I) and (II) are necessary components, and the structural units (III), (IV) and (V) are selected for formation, and the formation manners are respectively: (I), (II) and (IV); (I), (II), (III) and (IV); (I), and (II), (IV) and (V), wherein in the (I), (II), (III) and (V), R is an oxygen atom or methylene, R' is any one of an oxygen atom, a sulfur atom, methylene, -C(CH3)2- or -S(O)2-. The thermotropic liquid crystal random copolyester provided by the present invention further discloses a preparation method of the copolyester. By leading the kinking group components in the molecular main chains of the copolyester, the invention can not only greatly decrease the temperature of the liquid crystalline phase thereof, but also still maintain the thermal stability thereof. The preparation method of the invention is simple, and has easy operation and control, and good reproducibility.
Description
Technical field
The invention belongs to liquid crystal atactic polyester containing phosphor and preparing technical field thereof.Specifically, the present invention relates to the phosphorous of a kind of ternary or quaternary and kinking groups thermotropic liquid crystal random copolyester and preparation method thereof.This copolyesters has high flame retardant and thermotropic liquid crystal behavior, the halogen-free flame retardants that can be used as macromolecular material (as polymkeric substance such as polyester, polyolefine, nylon) uses, have characteristics such as nontoxic, efficient, that refractory drips, particularly can be under suitable forming process condition by fire-retardant polymkeric substance in-situ fibrillation, realize simultaneously fire-retardant and enhancing modified to macromolecular material.
Background technology
Over nearly 50 years, synthesized polymer material is owing to have light weight, excellent mechanical property, good formability, film-forming properties, insulativity and resistance to acids and bases, and characteristics such as low ventilative, water-permeable, easy coloring, outward appearance be bright-coloured, be widely applied in the every field and daily life of national economy.But most of macromolecular materials are because of all being elementary composition by C, H, three kinds of O, so at high temperature not only easily decompose, burn, and in combustion processes, also can produce a large amount of dense smoke and toxic and harmful, to ecotope and people's the healthy huge harm that causes.
Be conservation of nature ecotope and human health, people are to the flame-retardant modified extensive studies of having carried out of macromolecular material.
At present, the common flame-retardant modified method of macromolecular material mainly contains two kinds: fire-retardant method of body and blending method.The fire-retardant method of body is to add the monomer with flame retardant resistance in the polymeric process, introduces ignition-proof element and obtain flame retardant resistance on polymer molecular chain.Though the fire-retardant method of body can be given the macromolecular material flame retardant properties, technology relative complex, cost are higher, and fire-retardant monomeric content after a little while, do not reach fire-retardant requirement, during too high levels, can cause the change significantly of the original performance of macromolecular material again.Blending method is to add fire retardant in polymer processing, thereby reaches the method for improving the macromolecular material flame retardant properties.Blending method has advantages such as technology is simple, flame retardant properties excellence.Existing commercialization flame retarded polymeric material mainly adopts blending method.But blending method also has some shortcomings to need to be resolved hurrily, can cause the decline of material mechanical performance as interface interaction poor between fire retardant and the macromolecular material, be not suitable for the application of special dimension, also have the fire retardant that adds to move gradually along with the loss of time, cause flame retardant properties to descend.
Advantages such as Thermotropic Liquid (TLCP) has high strength, high-modulus, linear expansivity is little, resistance toheat good, acid and alkali-resistance and resistance to chemical attack, and can reduce the melt viscosity of matrix material with the macromolecular material blend, improve the processing characteristics of macromolecular material.Moreover, under the effect of stress field, TLCP can also form fento in polymeric matrix, play the enhanced effect in the course of processing, forms in-situ composite.If give TLCP flame retardant resistance, then can in the mechanical property that improves the blend macromolecular material, give its corresponding flame retardant resistance, enlarge the application of macromolecular material in more areas.
At present, be devoted to the scientific worker of TLCP research, its focus mainly concentrates on and how to promote TLCP to form aspect the fento in polymeric matrix, and research TLCP uses aspect fire-retardant seldom.This mainly is because the melt temperature of TLCP is higher, does not match with the processing temperature of a lot of polymkeric substance.Inventor Yu-Zhong Wang was at " Journal of Material Chemistry " Vol.13 in 2003; No.6; once reported among the PP.1248-1249 and used the acetylize P-hydroxybenzoic acid; terephthalic acid; acetylizad 9; the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene-Resorcinol of 10-phosphinylidyne is a monomer synthetic phosphor-containing flame-proof Thermotropic Liquid; this phosphor-containing flame-proof Thermotropic Liquid not only has good thermostability and flame retardant resistance; and the mechanical property and the flame retardant properties of the in-situ composite of this TLCP and polyester blend preparation all are improved, and have solved polyester flame-retardant and have strengthened conflicting problem.Yet because the liquid crystal phase transition temperature of this TLCP is higher than 290 ℃, still do not match,, do not reach the enhanced purpose so can not under the processing temperature of most of thermoplastic resins, prepare in-situ composite with the processing temperature of most of thermoplastic resins.If be higher than the processing temperature processing of thermoplastic resin, thermoplastic resin can take place to decompose or oxidation, and performance also can be had a strong impact on.Therefore the melt temperature that reduces the phosphor-containing flame-proof Thermotropic Liquid just seems extremely important.To this, the inventor is by further research, a kind of phosphor-containing flame-proof Thermotropic Liquid that can be complementary with most of thermoplastic resin processing temperatures and preparation method thereof (CN1749294A) disclosed, this method mainly is to reduce its melt temperature by introduce flexible chain on the TLCP main chain, but the flexible chain of regrettably introducing can cause the decline of TLCP thermostability.
Summary of the invention
The objective of the invention is defective at prior art, a kind of phosphorous and kinking groups thermotropic liquid crystal random copolyester is provided, this copolyesters not only melt temperature is low, can be complementary with most of thermoplastic resin processing temperatures, and can avoid main chain to contain the problem that flexible chain causes the TLCP thermostability to descend.
Another object of the present invention provides a kind of preparation method who prepares above-mentioned flame retardant type thermotropic liquid crystal random copolyester.
Phosphorous and kinking groups thermotropic liquid crystal random copolyester provided by the invention, it is characterized in that this copolyesters forms by following structural unit is random, wherein structural unit [I], [II] are necessary the composition, and [III] [IV], [V] form for selecting, and the composition mode is [I], [II] and [IV]; [I], [II], [III] and [IV]; [I], [II], [IV] and [V]; [I], [II], [III] and [V]:
R in the formula is Sauerstoffatom or methylene radical, R ' be Sauerstoffatom, sulphur atom, methylene radical ,-C (CH
3)
2-or-S (O)
2-in any.
In the copolyesters that [I], [II] and [IV] form, the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of the molfraction of [II]/[IV], and each structural unit is connected arbitrarily by the functional group of carboxyl and ester group.
In the copolyesters that [I], [II], [III] and [IV] form, the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of the molfraction of [II]/{ [III]+[IV] }, molfraction=1/9～9/1 of the molfraction of [III]/[IV], each structural unit is connected arbitrarily by the functional group of carboxyl and ester group.
In the copolyesters that [I], [II], [IV] and [V] form, the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of molfraction/[IV] of { [II]+[V] }, molfraction=1/9～9/1 of the molfraction of [II]/[V], each structural unit is connected arbitrarily by the functional group of carboxyl and ester group.
In the copolyesters that [I], [II], [III] and [V] form, the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of molfraction/[III] of { [II]+[V] }, molfraction=1/9～9/1 of the molfraction of [II]/[V], each structural unit is connected arbitrarily by the functional group of carboxyl and ester group.
The method of the phosphorous and kinking groups thermotropic liquid crystal random copolyester that preparation provided by the invention is above-mentioned, this method be earlier with reaction monomers under vacuum condition, in 60～100 ℃ of dryings 8～12 hours; Then with the reaction monomers selected for use with catalyzer, under the nitrogen atmosphere protection, stir and heat up in 200～340 ℃ of internal reactions 2～5 hours; Stop logical nitrogen, vacuumize then, and the continuation reaction stops heating after 0.5～2.5 hour in 270～340 ℃, is cooled to room temperature and promptly gets product.
The concrete structure of the used reaction monomers of this method is as follows:
R in the formula is Sauerstoffatom or methylene radical, R ' be Sauerstoffatom, sulphur atom, methylene radical ,-C (CH
3)
2-or-S (O)
2-in any.
More than the monomer of used structural formula [I] be the acetylize P-hydroxybenzoic acid; The monomer of used structural formula [II] is acetylize 9, and the 10-dihydro-9-oxy is mixed-the assorted phenanthrene-Resorcinol of 10-phosphinylidyne; The monomer of used structural formula [III] is a terephthalic acid; The monomer of used structural formula [IV] is specially such two kinds: 4, and 4 '-dioctyl phthalate phenyl ether, 4,4 '-dioctyl phthalate ditane; The monomer of used structural formula [V] is specially several like this: acetylize 4,4 '-dihydroxy diphenyl ether, acetylize 4, the different propane of 4 '-dihydroxyl hexichol; acetylize 4,4 '-dihydroxy diphenylsulphone, acetylize 4; 4 '-dioxydiphenyl methane, acetylize 4,4 '-dihydroxyl diphenyl sulfide.
When the reaction monomers of wherein selecting for use was [I] [II] and [IV], the molfraction of [I] accounted for 30～70% of all structural units, molfraction=1～1.2/1 of the molfraction of [II]/[IV].When the reaction monomers of selecting for use is [I], [II], [III] and [IV], the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of the molfraction of [II]/{ [III]+[IV] }, molfraction=1/9～9/1 of the molfraction of [III]/[IV].When the reaction monomers of selecting for use is [I], [II], [IV] and [V], the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of molfraction/[IV] of { [II]+[V] }, molfraction=1/9～9/1 of the molfraction of [II]/[V].When the reaction monomers of selecting for use is [I], [II], [III] and [V], the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of molfraction/[III] of { [II]+[V] }, molfraction=1/9～9/1 of the molfraction of [II]/[V].
Wherein the amount of added catalyzer is for pressing 0.01～0.1% of reaction monomers gross weight.
The used catalyzer of this method is any in antimonous oxide, zinc acetate, tetrabutyl titanate, manganese acetate, dialkyltin, the antimony glycol.
Compared with the prior art the present invention has the following advantages:
1, because the present invention has introduced the kinking groups composition on phosphorous liquid crystal copolyester molecular backbone chain, thereby improved the molecular chain rigidity of thermotropic liquid crystalline polymer to a certain extent, make the temperature of its mesomorphic phase greatly reduce, can with most of thermoplastic resins, processing temperature as PET, PBT, PC, PA is complementary, make them the time, can play better fire-retardant and enhancement matrix resin with these thermoplastic resins.
2, because the full aromatic ring monomer that contains kinking groups that the present invention introduces all has good thermostability, so though reduced the mesomorphic phase temperature of thermotropic liquid crystalline polymer, its thermostability still can keep.
3, preparation method of the present invention simple, be easy to operate and control favorable reproducibility.
Description of drawings
Fig. 1 is heated to 270 ℃ of gained photos for the embodiment of the invention 1 prepared liquid crystal atactic polyester film on hot platform polarizing microscope; Fig. 2 is heated to 260 ℃ of gained photos for the embodiment of the invention 7 prepared liquid crystal atactic polyester films on hot platform polarizing microscope; Fig. 3 is heated to 260 ℃ of gained photos for the embodiment of the invention 15 prepared liquid crystal atactic polyester films on hot platform polarizing microscope; Fig. 4 is heated to 260 ℃ of gained photos for the embodiment of the invention 22 prepared liquid crystal atactic polyester films on hot platform polarizing microscope; Fig. 5 is heated to 260 ℃ of gained photos for the embodiment of the invention 30 prepared liquid crystal atactic polyester films on hot platform polarizing microscope; Fig. 6 is heated to 260 ℃ of gained photos for the embodiment of the invention 39 prepared liquid crystal atactic polyester films on hot platform polarizing microscope.
Embodiment
Embodiment given below is to specific descriptions of the present invention, is necessary to be pointed out that at this following examples only are used for that the present invention is further illustrated, can not be interpreted as limiting the scope of the invention.If the person skilled in art according to the present invention content the present invention is made some nonessential improvement and adjustment, still belong to protection domain of the present invention.
In addition, what deserves to be explained is that the intrinsic viscosity of following examples products therefrom is to be phenol/tetrachloroethane mixed solvent of 1: 1 with mass ratio, records in 30 ℃.
Embodiment 1
Earlier reaction monomers is placed in the vacuum drying oven, after 60 ℃ of bakings were taken out in 12 hours, take by weighing acetylize P-hydroxybenzoic acid 5.40g (0.030mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 14.28g (0.035mol), 4,4 '-dioctyl phthalate phenyl ether 9.03g (0.035mol) and antimonous oxide 0.0029g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 4 hours of heating up in 200～330 ℃; Stop logical nitrogen, vacuumize then, and in 330～340 ℃, continue altogether to react to stop heating after 1.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.57dL/g.
Embodiment 2
Earlier reaction monomers is placed in the vacuum drying oven, after 80 ℃ of bakings were taken out in 10 hours, take by weighing acetylize P-hydroxybenzoic acid 7.20g (0.040mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 12.84g (0.0315mol), 4,4 '-dioctyl phthalate phenyl ether 7.37g (0.0286mol) and tetrabutyl titanate 0.0082g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 2 hours of heating up in 200～330 ℃; Stop logical nitrogen, vacuumize then, and in 330～340 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.84dL/g.
Embodiment 3
Earlier reaction monomers is placed in the vacuum drying oven, after 100 ℃ of bakings were taken out in 8 hours, take by weighing acetylize P-hydroxybenzoic acid 9.00g (0.050mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 10.20g (0.025mol), 4,4 '-dioctyl phthalate ditane 6.40g (0.025mol) and zinc acetate 0.0102g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 5 hours of heating up in 200～300 ℃; Stop logical nitrogen, vacuumize then, and in 300～340 ℃, continue altogether to react to stop heating after 2.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.79dL/g.
Embodiment 4
Earlier reaction monomers is placed in the vacuum drying oven, after 70 ℃ of bakings were taken out in 12 hours, take by weighing acetylize P-hydroxybenzoic acid 10.8g (0.060mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 8.75g (0.0214mol), 4,4 '-dioctyl phthalate phenyl ether 4.80g (0.0186mol) and tetrabutyl titanate 0.0122g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 5 hours of heating up in 200～330 ℃; Stop logical nitrogen, vacuumize then, and in 330～340 ℃, continue altogether to react to stop heating after 0.5 hour, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.75dL/g.
Embodiment 5
Earlier reaction monomers is placed in the vacuum drying oven, after 90 ℃ of bakings were taken out in 11 hours, take by weighing acetylize P-hydroxybenzoic acid 11.7g (0.065mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 7.752g (0.019mol), 4,4 '-dioctyl phthalate ditane 4.096g (0.016mol) and zinc acetate 0.0165g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 3.5 hours of heating up in 200～310 ℃; Stop logical nitrogen, vacuumize then, and in 310～340 ℃, continue altogether to react to stop heating after 2 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.87dL/g.
Embodiment 6
Earlier reaction monomers is placed in the vacuum drying oven, after 80 ℃ of bakings were taken out in 12 hours, take by weighing acetylize P-hydroxybenzoic acid 12.6g (0.070mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 6.12g (0.015mol), 4,4 '-dioctyl phthalate ditane 3.84g (0.015mol) and antimonous oxide 0.0226g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 4.5 hours of heating up in 200～270 ℃; Stop logical nitrogen, vacuumize then, and in 270～340 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.91dL/g.
Embodiment 7
Earlier reaction monomers is placed in the vacuum drying oven, after 70 ℃ of bakings were taken out in 12 hours, take by weighing acetylize P-hydroxybenzoic acid 5.40g (0.030mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 14.28g (0.035mol), terephthalic acid 5.229g (0.0315mol), 4,4 '-dioctyl phthalate phenyl ether 0.903g (0.0035mol) and tetrabutyl titanate 0.0026g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 4.5 hours of heating up in 200～330 ℃; Stop logical nitrogen, vacuumize then, and in 330～340 ℃, continue altogether to react to stop heating after 1.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.77dL/g.
Embodiment 8
Earlier reaction monomers is placed in the vacuum drying oven, after 60 ℃ of bakings were taken out in 11 hours, take by weighing acetylize P-hydroxybenzoic acid 7.20g (0.040mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 13.09g (0.0321mol), terephthalic acid 3.86g (0.0233mol), 4,4 '-dioctyl phthalate ditane 1.20g (0.0047mol) and antimonous oxide 0.0076g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 4.0 hours of heating up in 200～330 ℃; Stop logical nitrogen, vacuumize then, and in 330～340 ℃, continue altogether to react to stop heating after 2.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 1.02dL/g.
Embodiment 9
Earlier reaction monomers is placed in the vacuum drying oven, after 80 ℃ of bakings were taken out in 10 hours, take by weighing acetylize P-hydroxybenzoic acid 9.00g (0.050mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene-Resorcinol 10.20 (0.025mol) of 10-phosphinylidyne, terephthalic acid 3.1125g (0.0188mol), 4, and 4 '-dioctyl phthalate phenyl ether 1.6125g (0.00625mol) and zinc acetate 0.0096g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 4.5 hours of heating up in 200～330 ℃; Stop logical nitrogen, vacuumize then, and in 300～340 ℃, continue altogether to react to stop heating after 2.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.68dL/g.
Embodiment 10
Earlier reaction monomers is placed in the vacuum drying oven, after 100 ℃ of bakings were taken out in 8 hours, take by weighing acetylize P-hydroxybenzoic acid 10.8g (0.060mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene-Resorcinol 8.90 (0.022mol) of 10-phosphinylidyne, terephthalic acid 1.511g (0.0091mol), 4, and 4 '-dioctyl phthalate ditane 2.33g (0.0091mol) and zinc acetate 0.0188g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 5.0 hours of heating up in 200～300 ℃; Stop logical nitrogen, vacuumize then, and in 330～340 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.87dL/g.
Embodiment 11
Earlier reaction monomers is placed in the vacuum drying oven, after 90 ℃ of bakings were taken out in 9 hours, take by weighing acetylize P-hydroxybenzoic acid 11.7g (0.065mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene-Resorcinol 7.55 (0.0185mol) of 10-phosphinylidyne, terephthalic acid 0.465g (0.00281mol), 4, and 4 '-dioctyl phthalate phenyl ether 3.612g (0.0014mol) and tetrabutyl titanate 0.0163g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 5.0 hours of heating up in 200～320 ℃; Stop logical nitrogen, vacuumize then, and in 320～340 ℃, continue altogether to react to stop heating after 1.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.96dL/g.
Embodiment 12
Earlier reaction monomers is placed in the vacuum drying oven, after 80 ℃ of bakings were taken out in 11 hours, take by weighing acetylize P-hydroxybenzoic acid 12.6g (0.070mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene-Resorcinol 6.12 (0.015mol) of 10-phosphinylidyne, terephthalic acid 0.249g (0.0015mol), 4, and 4 '-dioctyl phthalate ditane 3.456g (0.0135mol) and antimonous oxide 0.0224g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 5.0 hours of heating up in 200～270 ℃; Stop logical nitrogen, vacuumize then, and in 270～340 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.75dL/g.
Embodiment 13
Earlier reaction monomers is placed in the vacuum drying oven, after 70 ℃ of bakings were taken out in 12 hours, take by weighing acetylize P-hydroxybenzoic acid 5.40g (0.030mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 1.428g (0.0035mol), 4,4 '-dioctyl phthalate phenyl ether 9.03g (0.035mol), acetylize 4,4 '-dihydroxy diphenyl ether 9.01g (0.0315mol) and zinc acetate 0.0249g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 3.5 hours of heating up in 200～330 ℃; Stop logical nitrogen, vacuumize then, and in 330～340 ℃, continue altogether to react to stop heating after 1.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.51dL/g.
Embodiment 14
Earlier reaction monomers is placed in the vacuum drying oven, after 90 ℃ of bakings were taken out in 8 hours, take by weighing acetylize P-hydroxybenzoic acid 6.30g (0.035mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 1.714g (0.0042mol), 4,4 '-dioctyl phthalate phenyl ether 8.256g (0.032mol), acetylize 4, different propane 9.173g of 4 '-dihydroxyl hexichol (0.0294mol) and antimonous oxide 0.0204g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 4.5 hours of heating up in 200～300 ℃; Stop logical nitrogen, vacuumize then, and in 300～340 ℃, continue altogether to react to stop heating after 2.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.88dL/g.
Embodiment 15
Earlier reaction monomers is placed in the vacuum drying oven, after 80 ℃ of bakings were taken out in 9 hours, take by weighing acetylize P-hydroxybenzoic acid 7.20g (0.040mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 2.04g (0.005mol), 4,4 '-dioctyl phthalate phenyl ether 7.74g (0.030mol), acetylize 4,4 '-dihydroxy diphenylsulphone 8.35g (0.025mol) and tetrabutyl titanate 0.0152g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 4.0 hours of heating up in 200～330 ℃; Stop logical nitrogen, vacuumize then, and in 330～340 ℃, continue altogether to react to stop heating after 0.5 hour, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.97dL/g.
Embodiment 16
Earlier reaction monomers is placed in the vacuum drying oven, after 90 ℃ of bakings were taken out in 8.5 hours, take by weighing acetylize P-hydroxybenzoic acid 8.10g (0.045mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 2.938g (0.0072mol), 4,4 '-dioctyl phthalate phenyl ether 10.69g (0.0262mol), acetylize 4,4 '-dioxydiphenyl methane 6.142g (0.0216mol) and antimonous oxide 0.0111g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 4.5 hours of heating up in 200～270 ℃; Stop logical nitrogen, vacuumize then, and in 270～320 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.93dL/g.
Embodiment 17
Earlier reaction monomers is placed in the vacuum drying oven, after 100 ℃ of bakings were taken out in 8 hours, take by weighing acetylize P-hydroxybenzoic acid 9.00g (0.050mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 5.10g (0.0125mol), 4,4 '-dioctyl phthalate phenyl ether 6.45g (0.025mol), acetylize 4,4 '-dioxydiphenyl methane 3.775g (0.0125mol) and tetrabutyl titanate 0.0049g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 4.0 hours of heating up in 200～310 ℃; Stop logical nitrogen, vacuumize then, and in 310～340 ℃, continue altogether to react to stop heating after 1.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.96dL/g.
Embodiment 18
Earlier reaction monomers is placed in the vacuum drying oven, after 100 ℃ of bakings were taken out in 9 hours, take by weighing acetylize P-hydroxybenzoic acid 9.90g (0.055mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 7.344g (0.018mol), 4,4 '-dioctyl phthalate phenyl ether 5.39g (0.0209mol), acetylize 4,4 '-dihydroxy diphenyl ether 1.716g (0.0060mol) and zinc acetate 0.0024g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 5.0 hours of heating up in 200～320 ℃; Stop logical nitrogen, vacuumize then, and in 320～340 ℃, continue altogether to react to stop heating after 2.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.93dL/g.
Embodiment 19
Earlier reaction monomers is placed in the vacuum drying oven, after 85 ℃ of bakings were taken out in 10 hours, take by weighing acetylize P-hydroxybenzoic acid 10.8g (0.060mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 7.426g (0.0182mol), 4,4 '-dioctyl phthalate phenyl ether 4.70g (0.0182mol), acetylize 4, different propane 1.123g of 4 '-dihydroxyl hexichol (0.0036mol) and antimonous oxide 0.0064g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 2.0 hours of heating up in 200～280 ℃; Stop logical nitrogen, vacuumize then, and in 280～330 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.55dL/g.
Embodiment 20
Earlier reaction monomers is placed in the vacuum drying oven, after 90 ℃ of bakings were taken out in 10 hours, take by weighing acetylize P-hydroxybenzoic acid 11.7g (0.065mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 6.248g (0.0153mol), 4,4 '-dioctyl phthalate phenyl ether 4.52g (0.0175mol), acetylize 4,4 '-dihydroxy diphenylsulphone 0.731g (0.0022mol) and tetrabutyl titanate 0.0116g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 4.0 hours of heating up in 200～320 ℃; Stop logical nitrogen, vacuumize then, and in 320～340 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 1.08dL/g.
Embodiment 21
Earlier reaction monomers is placed in the vacuum drying oven, after 60 ℃ of bakings were taken out in 11 hours, take by weighing acetylize P-hydroxybenzoic acid 12.60g (0.070mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 5.508g (0.0135mol), 4,4 '-dioctyl phthalate phenyl ether 3.87g (0.015mol), acetylize 4,4 '-dioxydiphenyl methane 0.426g (0.0015mol) and zinc acetate 0.0202g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 5.0 hours of heating up in 200～330 ℃; Stop logical nitrogen, vacuumize then, and in 330～340 ℃, continue altogether to react to stop heating after 0.5 hour, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.77dL/g.
Embodiment 22
Earlier reaction monomers is placed in the vacuum drying oven, after 70 ℃ of bakings were taken out in 11 hours, take by weighing acetylize P-hydroxybenzoic acid 5.40g (0.030mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 12.69g (0.0311mol), 4,4 '-dioctyl phthalate ditane 8.96g (0.035mol), acetylize 4,4 '-dihydroxyl diphenyl sulfide 1.174g (0.0039mol) and tetrabutyl titanate 0.0056g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 2.5 hours of heating up in 200～300 ℃; Stop logical nitrogen, vacuumize then, and in 300～320 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.69dL/g.
Embodiment 23
Earlier reaction monomers is placed in the vacuum drying oven, after 80 ℃ of bakings were taken out in 12 hours, take by weighing acetylize P-hydroxybenzoic acid 6.30g (0.035mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 11.38g (0.0279mol), 4,4 '-dioctyl phthalate ditane 8.32g (0.0325mol), acetylize 4,4 '-dioxydiphenyl methane 1.306g (0.0046mol) and zinc acetate 0.0109g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 4.5 hours of heating up in 200～310 ℃; Stop logical nitrogen, vacuumize then, and in 310～330 ℃, continue altogether to react to stop heating after 1.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.85dL/g.
Embodiment 24
Earlier reaction monomers is placed in the vacuum drying oven, after 90 ℃ of bakings were taken out in 10 hours, take by weighing acetylize P-hydroxybenzoic acid 7.20g (0.040mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 10.45g (0.0256mol), 4,4 '-dioctyl phthalate ditane 7.07g (0.0276mol), acetylize 4,4 '-dihydroxy diphenylsulphone 2.14g (0.0064mol) and antimonous oxide 0.0134g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 5.0 hours of heating up in 200～270 ℃; Stop logical nitrogen, vacuumize then, and in 270～320 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.78dL/g.
Embodiment 25
Earlier reaction monomers is placed in the vacuum drying oven, after 60 ℃ of bakings were taken out in 10 hours, take by weighing acetylize P-hydroxybenzoic acid 8.10g (0.045mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 7.48g (0.0183mol), 4,4 '-dioctyl phthalate ditane 7.04g (0.0275mol), acetylize 4, different propane 2.86g of 4 '-dihydroxyl hexichol (0.0092mol) and tetrabutyl titanate 0.0076g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 4.0 hours of heating up in 200～320 ℃; Stop logical nitrogen, vacuumize then, and in 320～340 ℃, continue altogether to react to stop heating after 2.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.64dL/g.
Embodiment 26
Earlier reaction monomers is placed in the vacuum drying oven, after 70 ℃ of bakings were taken out in 11 hours, take by weighing acetylize P-hydroxybenzoic acid 9.00g (0.050mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 5.10g (0.0125mol), 4,4 '-dioctyl phthalate ditane 6.40g (0.025mol), acetylize 4,4 '-dihydroxy diphenyl ether 3.575g (0.0125mol) and antimonous oxide 0.0024g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 4.5 hours of heating up in 200～330 ℃; Stop logical nitrogen, vacuumize then, and in 330～340 ℃, continue altogether to react to stop heating after 1.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.98dL/g.
Embodiment 27
Earlier reaction monomers is placed in the vacuum drying oven, after 80 ℃ of bakings were taken out in 12 hours, take by weighing acetylize P-hydroxybenzoic acid 9.90g (0.055mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 2.295g (0.0056mol), 4,4 '-dioctyl phthalate ditane 5.76g (0.0225mol), acetylize 4,4 '-dihydroxy diphenylsulphone 5.645g (0.0169mol) and zinc acetate 0.0165g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 5.0 hours of heating up in 200～300 ℃; Stop logical nitrogen, vacuumize then, and in 300～340 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.86dL/g.
Embodiment 28
Earlier reaction monomers is placed in the vacuum drying oven, after 90 ℃ of bakings were taken out in 8 hours, take by weighing acetylize P-hydroxybenzoic acid 10.8g (0.060mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 1.469g (0.0036mol), 4,4 '-dioctyl phthalate ditane 4.654g (0.0182mol), acetylize 4,4 '-dihydroxyl diphenyl sulfide 5.50g (0.0182mol) and tetrabutyl titanate 0.0202g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 3.5 hours of heating up in 200～310 ℃; Stop logical nitrogen, vacuumize then, and in 310～330 ℃, continue altogether to react to stop heating after 2.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.82dL/g.
Embodiment 29
Earlier reaction monomers is placed in the vacuum drying oven, after 70 ℃ of bakings were taken out in 9 hours, take by weighing acetylize P-hydroxybenzoic acid 11.7g (0.065mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 0.938g (0.0023mol), 4,4 '-dioctyl phthalate ditane 4.096g (0.016mol), acetylize 4,4 '-dioxydiphenyl methane 4.57g (0.0161mol) and antimonous oxide 0.0170g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 5.0 hours of heating up in 200～270 ℃; Stop logical nitrogen, vacuumize then, and in 270～330 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 1.03dL/g.
Embodiment 30
Earlier reaction monomers is placed in the vacuum drying oven, after 60 ℃ of bakings were taken out in 12 hours, take by weighing acetylize P-hydroxybenzoic acid 12.60g (0.070mol), acetylize 9 respectively, the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 0.612g (0.0015mol), 4,4 '-dioctyl phthalate ditane 3.84g (0.015mol), acetylize 4, different propane 4.212g of 4 '-dihydroxyl hexichol (0.0135mol) and zinc acetate 0.0213g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 4.0 hours of heating up in 200～330 ℃; Stop logical nitrogen, vacuumize then, and in 330～340 ℃, continue altogether to react to stop heating after 1.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.75dL/g.
Embodiment 31
Earlier reaction monomers is placed in the vacuum drying oven, after 80 ℃ of bakings were taken out in 9 hours, take by weighing acetylize P-hydroxybenzoic acid 5.40g (0.030mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 1.428g (0.0035mol), terephthalic acid 5.81g (0.035mol), acetylize 4, and 4 '-dihydroxy diphenyl ether 9.01g (0.0315mol) and tetrabutyl titanate 0.0022g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 4.0 hours of heating up in 200～270 ℃; Stop logical nitrogen, vacuumize then, and in 270～300 ℃, continue altogether to react to stop heating after 2.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.79dL/g.
Embodiment 32
Earlier reaction monomers is placed in the vacuum drying oven, after 100 ℃ of bakings were taken out in 8 hours, take by weighing acetylize P-hydroxybenzoic acid 6.30g (0.035mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 1.673g (0.0041mol), terephthalic acid 5.395g (0.0325mol), acetylize 4, and different propane 8.861g of 4 '-dihydroxyl hexichol (0.0284mol) and zinc acetate 0.0067g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 4.5 hours of heating up in 200～310 ℃; Stop logical nitrogen, vacuumize then, and in 310～340 ℃, continue altogether to react to stop heating after 0.5 hour, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.98dL/g.
Embodiment 33
Earlier reaction monomers is placed in the vacuum drying oven, after 100 ℃ of bakings were taken out in 10 hours, take by weighing acetylize P-hydroxybenzoic acid 7.20g (0.040mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 2.12g (0.0052mol), terephthalic acid 4.71g (0.0284mol), acetylize 4, and 4 '-dihydroxy diphenylsulphone 8.68g (0.026mol) and antimonous oxide 0.0159g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 2.0 hours of heating up in 200～300 ℃; Stop logical nitrogen, vacuumize then, and in 300～340 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.64dL/g.
Embodiment 34
Earlier reaction monomers is placed in the vacuum drying oven, after 90 ℃ of bakings were taken out in 11 hours, take by weighing acetylize P-hydroxybenzoic acid 8.10g (0.045mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 2.805g (0.0069mol), terephthalic acid 4.565g (0.0275mol), acetylize 4, and 4 '-dioxydiphenyl methane 5.858g (0.0206mol) and zinc acetate 0.0213g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 3.5 hours of heating up in 200～300 ℃; Stop logical nitrogen, vacuumize then, and in 300～340 ℃, continue altogether to react to stop heating after 1.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.69dL/g.
Embodiment 35
Earlier reaction monomers is placed in the vacuum drying oven, after 80 ℃ of bakings were taken out in 10 hours, take by weighing acetylize P-hydroxybenzoic acid 9.00g (0.050mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 5.10g (0.0125mol), terephthalic acid 4.15g (0.025mol), acetylize 4, and 4 '-dihydroxyl diphenyl sulfide 3.775g (0.0125mol) and antimonous oxide 0.0176g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 5.0 hours of heating up in 200～320 ℃; Stop logical nitrogen, vacuumize then, and in 320～340 ℃, continue altogether to react to stop heating after 1.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.97dL/g.
Embodiment 36
Earlier reaction monomers is placed in the vacuum drying oven, after 60 ℃ of bakings were taken out in 12 hours, take by weighing acetylize P-hydroxybenzoic acid 9.90g (0.055mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 7.34g (0.018mol), terephthalic acid 3.469g (0.0209mol), acetylize 4, and 4 '-dihydroxy diphenyl ether 1.716g (0.0060mol) and tetrabutyl titanate 0.0112g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 2.5 hours of heating up in 200～280 ℃; Stop logical nitrogen, vacuumize then, and in 280～320 ℃, continue altogether to react to stop heating after 1.0 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.73dL/g.
Embodiment 37
Earlier reaction monomers is placed in the vacuum drying oven, after 70 ℃ of bakings were taken out in 11.5 hours, take by weighing acetylize P-hydroxybenzoic acid 10.8g (0.060mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 7.426g (0.0182mol), terephthalic acid 3.02g (0.0182mol), acetylize 4, and 4 '-dioxydiphenyl methane 1.022g (0.0036mol) and zinc acetate 0.0089g; Then with the reaction monomers that takes by weighing with zinc acetate, under the nitrogen atmosphere protection, stir the coreaction 3.0 hours of heating up in 200～300 ℃; Stop logical nitrogen, vacuumize then, and in 300～340 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.67dL/g.
Embodiment 38
Earlier reaction monomers is placed in the vacuum drying oven, after 90 ℃ of bakings were taken out in 10 hours, take by weighing acetylize P-hydroxybenzoic acid 11.7g (0.065mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 6.248g (0.0153mol), terephthalic acid 2.905g (0.0175mol), acetylize 4, and different propane 0.686g of 4 '-dihydroxyl hexichol (0.0022mol) and antimonous oxide 0.0194g; Then with the reaction monomers that takes by weighing with antimonous oxide, under the nitrogen atmosphere protection, stir the coreaction 3.5 hours of heating up in 200～300 ℃; Stop logical nitrogen, vacuumize then, and in 300～340 ℃, continue altogether to react to stop heating after 2.5 hours, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.93dL/g.
Embodiment 39
Earlier reaction monomers is placed in the vacuum drying oven, after 100 ℃ of bakings were taken out in 12 hours, take by weighing acetylize P-hydroxybenzoic acid 12.60g (0.070mol), acetylize 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 5.508g (0.0135mol), terephthalic acid 2.49g (0.015mol), acetylize 4, and 4 '-dihydroxyl diphenyl sulfide 0.453g (0.0015mol) and tetrabutyl titanate 0.0042g; Then with the reaction monomers that takes by weighing with tetrabutyl titanate, under the nitrogen atmosphere protection, stir the coreaction 5.0 hours of heating up in 200～270 ℃; Stop logical nitrogen, vacuumize then, and in 270～300 ℃, continue altogether to react to stop heating after 0.5 hour, be cooled to room temperature and promptly get product.
The intrinsic viscosity of this product is 0.62dL/g.
Obtain the performance of Thermotropic Liquid in order to investigate, liquid crystal liquid crystal property, thermal characteristics that the present invention has adopted the hot platform polarizing microscope of Leica DLMP type, TA Q200 type DSC tester and Netzsch TG209F1 type thermogravimetric analyzer to test copolyesters, and with JF-3 type oxygen index instrument, according to GB2406-80 and UL-94 standard testing the flame retardant properties of copolyesters, its result sees Fig. 1-6 and table 1,2 respectively.
Table 1
| Sample | T g(℃) | T m(℃) | ?T d5％(℃) | T max(℃) | 700 ℃ of following carbon residue amounts (%) |
| Embodiment 1 | 174.2 | 249 | ?434 | 480 | 49.36 |
| Embodiment 2 | 182.3 | 248 | ?436 | 489 | 49.01 |
| Embodiment 3 | 185.5 | 255 | ?442 | 492 | 47.13 |
| Embodiment 4 | 177.4 | 243 | ?431 | 476 | 46.25 |
| Embodiment 5 | 172.3 | 240 | ?437 | 482 | 44.18 |
| Embodiment 6 | 176.3 | 246 | ?445 | 487 | 43.56 |
| Embodiment 7 | 168.0 | 251 | ?465 | 500 | 51.28 |
| Embodiment 8 | 174.2 | 245 | ?469 | 502 | 51.64 |
| Embodiment 9 | 178.3 | 254 | ?472 | 506 | 47.86 |
| Embodiment 10 | 166.3 | 248 | ?457 | 486 | 44.62 |
| Embodiment 11 | 169.2 | 240 | ?461 | 489 | 44.37 |
| Embodiment 12 | 171.5 | 252 | ?467 | 495 | 43.32 |
| Embodiment 13 | 147.0 | 209 | ?432 | 481 | 51.78 |
| Embodiment 14 | 151.5 | 207 | ?449 | 487 | 52.63 |
| Embodiment 15 | 154.6 | 213 | ?455 | 491 | 37.96 |
| Embodiment 16 | 148.2 | 221 | ?457 | 482 | 38.72 |
| Embodiment 17 | 152.2 | 217 | ?452 | 485 | 39.21 |
| Embodiment 18 | 157.0 | 229 | ?443 | 489 | 44.39 |
Table 1 is continuous
| Sample | T g(℃) | T m(℃) | ?T d5％(℃) | T max(℃) | 700 ℃ of following carbon residue amounts (%) |
| Embodiment 19 | 142.1 | 217 | ?437 | 475 | 44.56 |
| Embodiment 20 | 147.2 | 213 | ?446 | 482 | 43.64 |
| Embodiment 21 | 150.2 | 221 | ?451 | 493 | 42.55 |
| Embodiment 22 | 158.4 | 235 | ?449 | 487 | 50.39 |
| Embodiment 23 | 159.0 | 228 | ?452 | 488 | 48.72 |
| Embodiment 24 | 162.5 | 239 | ?457 | 496 | 46.73 |
| Embodiment 25 | 147.3 | 219 | ?446 | 485 | 44.15 |
| Embodiment 26 | 151.2 | 218 | ?449 | 483 | 39.26 |
| Embodiment 27 | 157.6 | 234 | ?461 | 494 | 37.61 |
| Embodiment 28 | 139.9 | 196 | ?432 | 475 | 35.56 |
| Embodiment 29 | 142.3 | 201 | ?447 | 481 | 34.27 |
| Embodiment 30 | 146.0 | 214 | ?451 | 486 | 33.81 |
| Embodiment 31 | 151.3 | 236 | ?443 | 489 | 50.73 |
| Embodiment 32 | 154.6 | 232 | ?449 | 495 | 52.59 |
| Embodiment 33 | 162.5 | 241 | ?456 | 501 | 38.03 |
| Embodiment 34 | 147.6 | 228 | ?441 | 476 | 38.51 |
| Embodiment 35 | 148.7 | 225 | ?457 | 498 | 39.92 |
| Embodiment 36 | 152.0 | 237 | ?461 | 502 | 43.61 |
| Embodiment 37 | 147.3 | 225 | ?446 | 478 | 44.52 |
| Embodiment 38 | 151.3 | 219 | ?456 | 483 | 43.26 |
| Embodiment 39 | 156.9 | 231 | ?467 | 495 | 41.63 |
Annotate: T
mData are obtained by polarizing microscope.
Table 2
| Sample | Oxygen index | UL-94 vertical combustion grade | The fusion drippage |
| Embodiment 1 | 76.7 | V-0 | Do not have |
| Embodiment 2 | 73.3 | V-0 | Do not have |
| Embodiment 3 | 72.6 | V-0 | Do not have |
| Embodiment 4 | 65.1 | V-0 | Do not have |
| Embodiment 5 | 64.9 | V-0 | Do not have |
| Embodiment 6 | 62.3 | V-0 | Do not have |
| Embodiment 7 | 75.2 | V-0 | Do not have |
| Embodiment 8 | 73.0 | V-0 | Do not have |
| Embodiment 9 | 71.5 | V-0 | Do not have |
| Embodiment 10 | 70.9 | V-0 | Do not have |
| Embodiment 11 | 64.6 | V-0 | Do not have |
| Embodiment 12 | 61.2 | V-0 | Do not have |
| Embodiment 13 | 70.7 | V-0 | Do not have |
| Embodiment 14 | 77.4 | V-0 | Do not have |
| Embodiment 15 | 51.5 | V-0 | Do not have |
| Embodiment 16 | 53.3 | V-0 | Do not have |
| Embodiment 17 | 59.6 | V-0 | Do not have |
| Embodiment 18 | 61.6 | V-0 | Do not have |
| Embodiment 19 | 62.2 | V-0 | Do not have |
| Embodiment 20 | 61.8 | V-0 | Do not have |
| Embodiment 21 | 60.4 | V-0 | Do not have |
| Embodiment 22 | 73.2 | V-0 | Do not have |
| Embodiment 23 | 69.7 | V-0 | Do not have |
| Embodiment 24 | 70.4 | V-0 | Do not have |
| Embodiment 25 | 63.6 | V-0 | Do not have |
| Embodiment 26 | 60.8 | V-0 | Do not have |
Table 2 is continuous
| Sample | Oxygen index | UL-94 vertical combustion grade | The fusion drippage |
| Embodiment 27 | 53.1 | V-0 | Do not have |
| Embodiment 28 | 51.6 | V-0 | Do not have |
| Embodiment 29 | 48.9 | V-0 | Do not have |
| Embodiment 30 | 47.3 | V-0 | Do not have |
| Embodiment 31 | 72.8 | V-0 | Do not have |
| Embodiment 32 | 75.3 | V-0 | Do not have |
| Embodiment 33 | 52.5 | V-0 | Do not have |
| Embodiment 34 | 54.0 | V-0 | Do not have |
| Embodiment 35 | 63.8 | V-0 | Do not have |
| Embodiment 36 | 67.1 | V-0 | Do not have |
| Embodiment 37 | 68.6 | V-0 | Do not have |
| Embodiment 38 | 66.2 | V-0 | Do not have |
| Embodiment 39 | 64.9 | V-0 | Do not have |
By Fig. 1-6 as can be seen, this class is phosphorous to have typical nematic liquid crystal texture with liquid crystal copolyester kinking groups, and the copolyesters that provable thus the present invention obtains has liquid crystal liquid crystal property.Other embodiment also can observe similar nematic liquid crystal texture under hot platform polarizing microscope.
As can be seen from Table 1, the liquid crystal copolyester that the present invention obtains has high glass transition and heat decomposition temperature, and all is higher than 30% at 700 ℃ residual volume, illustrates that it has good thermostability and becomes carbon.As can be seen from Table 2, the limiting oxygen index(LOI) of the liquid crystal copolyester that the present invention obtains is all greater than 50, and the vertical combustion grade has all reached V-0, and does not have the fusion drip phenomenon, illustrates that such liquid crystal copolyester has good flame retardancy.
The fusing point of the liquid crystal copolyester that obtains from the present invention has in addition reduced manyly than the liquid crystal copolyester of not introducing kinking groups, thereby can be complementary with the processing temperature of most of thermoplastic resins.
Claims (3)
1. phosphorous and kinking groups thermotropic liquid crystal random copolyester, it is characterized in that this copolyesters forms by following structural unit is random, wherein structural unit [I], [II] are necessary the composition, and [III], [IV], [V] form for selecting, and the composition mode is [I], [II] and [IV]; [I], [II], [III] and [IV]; [I], [II], [IV] and [V]; [I], [II], [III] and [V]:
R in the formula is Sauerstoffatom or methylene radical, R ' be Sauerstoffatom, sulphur atom, methylene radical ,-C (CH
3)
2-or-S (O)
2-in any,
And in the copolyesters that [I], [II] and [IV] form, the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of the molfraction of [II]/[IV], and each structural unit is connected arbitrarily by the functional group of carboxyl and ester group; In the copolyesters that [I], [II], [III] and [IV] form, the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of the molfraction of [II]/{ [III]+[IV] }, molfraction=1/9～9/1 of the molfraction of [III]/[IV], each structural unit is connected arbitrarily by the functional group of carboxyl and ester group; In the copolyesters that [I], [II], [IV] and [V] form, the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of molfraction/[IV] of { [II]+[V] }, molfraction=1/9～9/1 of the molfraction of [II]/[V], each structural unit is connected arbitrarily by the functional group of carboxyl and ester group; In the copolyesters that [I], [II], [III] and [V] form, the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of molfraction/[III] of { [II]+[V] }, molfraction=1/9～9/1 of the molfraction of [II]/[V], each structural unit is connected arbitrarily by the functional group of carboxyl and ester group.
2. method for preparing the described phosphorous and kinking groups thermotropic liquid crystal random copolyester of claim 1, this method be earlier with reaction monomers under vacuum condition, in 60～100 ℃ of dryings 8～12 hours; Then with the reaction monomers selected for use with catalyzer, under the nitrogen atmosphere protection, stir and heat up in 200～340 ℃ of internal reactions 2～5 hours; Stop logical nitrogen, vacuumize then, and the continuation reaction stops heating after 0.5～2.5 hour in 270～340 ℃, is cooled to room temperature and promptly gets product, the concrete structure of reaction monomers is as follows:
R in the formula is Sauerstoffatom or methylene radical, R ' be Sauerstoffatom, sulphur atom, methylene radical ,-C (CH
3)
2-or-S (O)
2-in any,
When the reaction monomers of wherein selecting for use was [I], [II] and [IV], the molfraction of [I] accounted for 30～70% of all structural units, molfraction=1～1.2/1 of the molfraction of [II]/[IV]; When the reaction monomers of selecting for use is [I], [II], [III], [IV], the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of the molfraction of [II]/{ [III]+[IV] }, molfraction=1/9～9/1 of the molfraction of [III]/[IV]; When the reaction monomers of selecting for use is [I], [II], [IV], [V], the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of molfraction/[IV] of { [II]+[V] }, molfraction=1/9～9/1 of the molfraction of [II]/[V]; When the reaction monomers of selecting for use is [I], [II], [III], [V], the molfraction of [I] accounts for 30～70% of all structural units, molfraction=1～1.2/1 of molfraction/[III] of { [II]+[V] }, molfraction=1/9～9/1 of the molfraction of [II]/[V], wherein used catalyzer is for pressing 0.01～0.1% of reaction monomers gross weight.
3. the method for the phosphorous and kinking groups thermotropic liquid crystal random copolyester of preparation according to claim 2, the used catalyzer of this method is any in antimonous oxide, zinc acetate, tetrabutyl titanate, manganese acetate, dialkyltin, the antimony glycol.
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