CN100362037C - Liquid crystal atactic polyester containing phosphor and its preparing method - Google Patents
Liquid crystal atactic polyester containing phosphor and its preparing method Download PDFInfo
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Abstract
The present invention relates to liquid crystal atactic polyester containing phosphor and a preparing method. Acetylized p-Hydroxybenzoic acid, terephthalic acid, terephthalic acid alkyl radical alcohol ester, and acetylized 9, 10-dihydro-9-oxa-10-phosphoryl phenanthrene-hydroquinone are polymerized into the liquid crystal atactic polyester containing phosphor through the melt ester interchange reaction. The number of chain links of [I] in structural units of the copolyester is 30 to 70% of the number of chain links of all structural units. The ratio of the number of the chain links of [II] to the number of the chain links of [IV] is 0 to 9: 1. The ratio of the number of the chain links of{[II]+[IV]}to the number of the chain links of [III] is 1 to 1.2: 1. Chain sections or the chain links of four kinds of structural units can be arbitrarily connected and combined according to a carboxyl group and an oxhydryl functional group. Because the flexibility component of straight chain alkyl diol of which the carbon number is 2 to 6 is introduced on a molecular main chain, the temperature of the liquid crystal phase is greatly lowered. The processing temperature of most of thermoplastic resin can be matched, and the range of use is enlarged. The preparing method is simple and is easily controlled, the reaction speed is high, the time is short, the energy is saved, and the reproducibility is good.
Description
One, technical field
The invention belongs to liquid crystal atactic polyester containing phosphor and preparation method thereof technical field.Specifically, the present invention relates to a kind of quaternary liquid crystal atactic polyester containing phosphor and preparation method thereof.This copolyesters has the Halogen of the halogen-free flame retardants of liquid crystal liquid crystal property, nontoxic, efficient, the anti-characteristics such as drip of melting, and can be used for the flame-retardant modified of polymkeric substance such as polyester, Resins, epoxy, nylon.
Two, background technology
Along with the continuous development of science and technology, the human living standard improves constantly, and macromolecular material has obtained application more and more widely, has related to human clothing, food, lives, all respects of row, brings great convenience for people's life.But most macromolecular materials all are elementary composition by C, H, three kinds of O, and they all have a common characteristic is exactly flammable, inflammable.Therefore, in recent years, more and more because of the catch fire fire that causes of macromolecular material, this had not only caused tremendous loss to country, had brought huge threat also for simultaneously people's life security.
Fire takes place frequently day by day, people is more and more recognized macromolecular material is carried out fire-retardantization modification, is to reduce the important measures that fire takes place.
At present, be based on copolymerization method and blending method to the flame-retardant modified of macromolecular material.Copolymerization method normally makes the target macromolecular material obtain flame retardant resistance the method for a kind of monomer that contains ignition-proof element by copolymerization.Though this method can be given the flame retardant properties of target macromolecular material, but this monomer that contains ignition-proof element is few at target macromolecular material kind content, the fire-retardant requirement of inaccessible national standard defined, content is many and inevitably will change original performance of macromolecular material greatly.Therefore, in commercial flame retarded polymeric material, major part is that the method by blend makes macromolecular material obtain flame retardant resistance.Though blending method can be given target macromolecular material good flame retardant property, but for the flame retarded polymeric material system of major part by the blend gained, because the consistency of fire retardant and matrix is relatively poor, micron-scale phase separation takes place easily, thereby can reduce the mechanical property of material greatly.
As everyone knows, thermotropic liquid crystalline polymer has many good performances, as good processing properties, mechanical property and thermostability etc., its inherent intensity and rigidity in addition, make it in the melt-processed process, in field of flow, form fento easily, so can play the enhanced effect to substrate macromolecule material.Therefore research and development have the thermotropic liquid crystalline polymer fire retardant of good flame-retardance, to carry out melt blending with thermal plastic high polymers such as polyester, nylon, Resins, epoxy, through extrusion molding, injection moulding and prepare the in-situ micro-fibril matrix material, be one and can either give the thermal plastic high polymer good flame retardancy, do not influence the solution route of the mechanical property of thermal plastic high polymer again.For this reason, many scientific workers are being devoted to the research of fire-retardant thermotropic liquid crystalline polymer.Inventor Yu-Zhong Wang reported with acetylated P-hydroxybenzoic acid, terephthalic acid and acetylated 9 at Journal of MaterialChemistry Vol.13 No.6 pp.1248-1249 (2003), and the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene-Resorcinol of 10-phosphinylidyne is that monomer has synthesized a kind of phosphorous Thermotropic Liquid.This copolyesters is because of having good thermostability and flame retardant resistance, and with the in-situ composite of this polymer and polyester blend preparation, reaches simultaneously to strengthen and fire retardation, solved the enhancing and the fire-retardant conflicting difficult problem (CN1436811A) of polyester.Yet because the strong rigidity of the molecular chain of this thermotropic liquid crystalline polymer, make the temperature of its mesomorphic phase be higher than 290 ℃, do not match with the processing temperature of most of thermoplastic resins, when preparing the flame retardant resistance in-situ composite with it and thermoplastic resin, if be higher than processing and preparing in-situ composite under the processing temperature of thermoplastic resin, then can cause the part of thermoplastic resin to be decomposed or partial oxidation, its performance is had a strong impact on; If processing temperature at thermoplastic resin, promptly be lower than under the mesomorphic phase temperature of thermotropic liquid crystalline polymer and process, then can not play matrix resin is produced lubricated effect, the processing characteristics of thermoplastic resin can not get improving, also be difficult to in-situ fibrillation matrix resin is played the enhanced effect, therefore the application of the flame retardant resistance liquid crystal polymer of high mesomorphic phase temperature is greatly limited.In order to enlarge the Application Areas of flame retardant resistance liquid crystal polymer, the mesomorphic phase temperature that reduces the flame retardant resistance liquid crystal polymer just becomes extremely important.
Three, summary of the invention
The objective of the invention is defective at prior art, provide a kind of can liquid crystal atactic polyester containing phosphor that be complementary with the processing temperature of most of thermoplastic resins, new.
Another object of the present invention provides the method for this new liquid crystal atactic polyester containing phosphor of preparation.
Liquid crystal atactic polyester containing phosphor provided by the invention is characterized in that this copolyesters is made up of the structural unit of following [I], [II], [III], [IV] expression:
Wherein the structural unit number of [I] accounts for 30～70% of all structural unit numbers, the structural unit number of [II]: structural unit number=0～9 of [IV]: 1, the structural unit number of { [II]+[IV] }: structural unit number=1～1.2 of [III]: 1, the segment of four kinds of structural units or its formation can be connected combination arbitrarily with hydroxy functional group by carboxyl, and the R in [III] formula represents that carbonatoms is 2～6 straight chained alkyl.
The preparation method of above-mentioned liquid crystal atactic polyester containing phosphor provided by the invention; it is characterized in that this method is with following structure monomer; be acetylated P-hydroxybenzoic acid (A), terephthalic acid (B), terephthalic acid alkyl alcohol ester (C) and acetylated 9; the 10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol diethyl ester (D), is polymerized by melting state transesterification reaction:
R represents that carbonatoms is 2～6 straight chained alkyl in the formula, and concrete processing step is earlier starting monomer to be placed in the vacuum drying oven, dries by the fire 8～12 hours down in 60～100 ℃; Pressing monomer (A) again is all monomeric molar percentages 30～70%, the mol ratio of monomer (B) and monomer (C) is (B): (C)=0～9: 1, the mol ratio of the total amount of monomer (B) and monomer (C) and monomer (D) is (B+C): (D)=1～1.2: 1 proportioning weighing, and catalyzer is by being all starting monomer weight percent 0.01～0.1% weighings; Join in the reactor that has agitator with catalyzer then, feed nitrogen, under nitrogen protection, stirring heating heats up, and coreaction is 2～4.5 hours in 200～290 ℃ of temperature ranges; Stop logical nitrogen, begin then to vacuumize, be difficult for the small molecule by-product acetate of overflowing to remove, and continue to heat up and in 270～320 ℃ of temperature ranges, continue reaction totally 0.5～2.5 hour, stop heating, be cooled to room temperature, promptly get the beige product.
Wherein used catalyzer is selected from any in antimonous oxide, tetrabutyl titanate, four titanium oxide, manganese acetate, the dialkyltin antimony glycol.Preferred antimonous oxide, tetrabutyl titanate, antimony glycol.
Compared with the prior art the present invention has the following advantages:
1, because the present invention has introduced the flexible composition that carbonatoms is 2～6 straight chained alkyl glycol on phosphorous liquid crystal copolyester molecular backbone chain, thereby improved the strong rigidity of the molecular chain of thermotropic liquid crystalline polymer to a certain extent, make the temperature of its mesomorphic phase greatly reduce (seeing Table 1), can with most of thermoplastic resins, processing temperature as PET, PBT, PC, nylon, Resins, epoxy etc. is complementary, make it when preparing in-situ composite, can play better fire-retardant and enhancement matrix resin with these thermoplastic resins.
2, the monomer (B) that uses owing to the present invention can be dissolved in the melt of monomer (C), thereby makes that entire reaction speed is fast, not only can obtain the polymerisate of higher inherent viscosity in the short period of time, has also shortened the reaction times, has saved the energy.
3, preparation method of the present invention is simple, is easy to control, favorable reproducibility.
Four, description of drawings
Gained photo when the film that Fig. 1 makes for the embodiment of the invention 1 products therefrom is heated to 260 ℃ on hot platform polarizing microscope;
Fig. 2 is the enlarged photograph of Fig. 1 institute favored area.
Five, embodiment
Also the invention will be further described to provide embodiment below.Be necessary to be pointed out that at this following examples can not be interpreted as limiting the scope of the invention; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to protection domain of the present invention.
Embodiment 1
Earlier starting monomer is placed in the vacuum drying oven, after 60 ℃ of bakings were taken out in 12 hours, take by weighing acetylated P-hydroxybenzoic acid 5.40g (0.030mol), ethylene glycol terephthalate 12.53g (0.035mol), acetylated 9 respectively, under the 10-dihydro-9-oxy assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 14.28g (0.035mol) and antimonous oxide 0.0032g; Join in the reaction flask that has import and export of nitrogen and mechanical stirrer with antimonous oxide then, feed nitrogen, stirring heating heats up under nitrogen protection, makes system coreaction 2.5h in 210～280 ℃ of temperature ranges; Stop logical nitrogen, use oil pump instead and vacuumize, and continue to heat up and in 280～290 ℃ of temperature ranges, continue reaction 0.5h altogether, stop heating, be cooled to room temperature, promptly get the beige product.To take out product, be that phenol/tetrachloroethane mixed solvent of 1: 1 is made solvent with mass ratio, and the limiting viscosity that records product when 30 ℃ of temperature is [η]=0.61dL/g.
Embodiment 2
Earlier with starting monomer in vacuum drying oven, after 80 ℃ of bakings were taken out in 10 hours, taking by weighing acetylated P-hydroxybenzoic acid 7.20g (0.040mol), terephthalic acid 4.15g (0.025mol), mutual-phenenyl two acid bromide two alcohol ester 1.93g (0.0050mol), acetylated 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 12.24g (0.030mol) and antimonous oxide 0.0077g; Join in the reaction flask that has import and export of nitrogen and mechanical stirrer with antimonous oxide then, feed nitrogen, stirring heating heats up under nitrogen protection, makes system coreaction 2.0h in 200～270 ℃ of temperature ranges; Stop logical nitrogen, use oil pump instead and vacuumize, and continue to heat up and in 270～300 ℃ of temperature ranges, continue reaction 1.5h altogether, stop heating, be cooled to room temperature, promptly get the beige product.To take out product, be that phenol/tetrachloroethane mixed solvent of 1: 1 is made solvent with mass ratio, and the limiting viscosity that records product when 30 ℃ of temperature is [η]=0.82dL/g.
Embodiment 3
Earlier with starting monomer in vacuum drying oven, after 90 ℃ of bakings were taken out in 9 hours, taking by weighing acetylated P-hydroxybenzoic acid 9.0g (0.050mol), terephthalic acid 3.65g (0.023mol), terephthalic acid hexylene glycol ester 1.24g (0.0030mol), acetylated 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 9.79g (0.024mol) and antimony glycol 0.0118g; Join in the reaction flask that has import and export of nitrogen and mechanical stirrer with antimony glycol then, feed nitrogen, stirring heating heats up under nitrogen protection, makes system coreaction 2.5h in 240～290 ℃ of temperature ranges; Stop logical nitrogen, use oil pump instead and vacuumize, and continue to heat up and in 290～300 ℃ of temperature ranges, continue reaction 1.5h altogether, stop heating, be cooled to room temperature, promptly get the beige product.To take out product, be that phenol/tetrachloroethane mixed solvent of 1: 1 is made solvent with mass ratio, and the limiting viscosity that records product when 30 ℃ of temperature is [η]=0.91dL/g.
Embodiment 4
Earlier with starting monomer in vacuum drying oven, after 70 ℃ of bakings were taken out in 11 hours, taking by weighing acetylated P-hydroxybenzoic acid 10.80g (0.060mol), terephthalic acid 1.83g (0.011mol), ethylene glycol terephthalate 3.94g (0.011mol), acetylated 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 7.42g (0.018mol) and tetrabutyl titanate 0.0168g; Join in the reaction flask that has import and export of nitrogen and mechanical stirrer with tetrabutyl titanate then, feed nitrogen, stirring heating heats up under nitrogen protection, makes system coreaction 4.5h in 210～280 ℃ of temperature ranges; Stop logical nitrogen, use oil pump instead and vacuumize, and continue to heat up and in 280～290 ℃ of temperature ranges, continue reaction 2.5h altogether, stop heating, be cooled to room temperature, promptly get the beige product.To take out product, be that phenol/tetrachloroethane mixed solvent of 1: 1 is made solvent with mass ratio, and the limiting viscosity that records product when 30 ℃ of temperature is [η]=1.65dL/g.
Embodiment 5
Earlier with starting monomer in vacuum drying oven, after 100 ℃ of bakings were taken out in 8.5 hours, taking by weighing acetylated P-hydroxybenzoic acid 8.10g (0.045mol), terephthalic acid 3.49g (0.021mol), propylene glycol ester terephthalate 2.60g (0.007mol), acetylated 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol diethyl ester 11.02g (0.027mol) and tetrabutyl titanate 0.0227g; Join in the reaction flask that has import and export of nitrogen and mechanical stirrer with tetrabutyl titanate then, feed nitrogen, stirring heating heats up under nitrogen protection, makes system coreaction 4.0h in 240～290 ℃ of temperature ranges; Stop logical nitrogen, use oil pump instead and vacuumize, and continue to heat up and in 290～300 ℃ of temperature ranges, continue reaction 2.0h altogether, stop heating, be cooled to room temperature, promptly get the beige product.To take out product, be that phenol/tetrachloroethane mixed solvent of 1: 1 is made solvent with mass ratio, and the limiting viscosity that records product when 30 ℃ of temperature is [η]=1.12dL/g.
Embodiment 6
Earlier with starting monomer in vacuum drying oven, after 75 ℃ of bakings were taken out in 10.5 hours, taking by weighing acetylated P-hydroxybenzoic acid 9.90g (0.055mol), terephthalic acid 2.66g (0.016mol), terephthalic acid pentadiol ester 3.20g (0.008mol), acetylated 9 respectively, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Resorcinol 8.57g (0.021mol) and antimony glycol 0.0243g; Join in the reaction flask that has import and export of nitrogen and mechanical stirrer with antimony glycol then, feed nitrogen, stirring heating heats up under nitrogen protection, makes system coreaction 3.0h in 210～280 ℃ of temperature ranges; Stop logical nitrogen, use oil pump instead and vacuumize, and continue to heat up and in 280～290 ℃ of temperature ranges, continue reaction 2.0h altogether, stop heating, be cooled to room temperature, promptly get the beige product.To take out product, be that phenol/tetrachloroethane mixed solvent of 1: 1 is made solvent with mass ratio, and the limiting viscosity that records product when 30 ℃ of temperature is [η]=1.35dL/g.
In order to investigate the performance of liquid crystalline polymers that the present invention obtains, the liquid crystal liquid crystal property of this polymkeric substance that adopted the hot platform microscopic examination of Leica DLMP type polarisation; The thermal characteristics that adopts DuPont 2100 type DSC and DuPont 2001 type thermogravimetric analyzers to test this polymkeric substance; Adopt JF-3 type oxygen index instrument, and according to GB2406-80 standard and UL-94 standard testing the oxygen index and the vertical combustion of this polymkeric substance.The result sees Fig. 1,2 and table 1,2 respectively.
Table 1
| Sample | Tg(℃) | Tm(℃) | Ti(℃) | Td5％(℃) | Tmax(℃) | Carbon forming rate in the time of 650 ℃ (%) |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 | 149 141 129 151 142 145 | 247 239 228 253 213 205 | 345 331 313 350 317 301 | 405 400 403 402 406 394 | 462 459 465 468 465 455 | 33.93 33.12 34.12 31.03 31.59 30.06 |
Table 2
| Sample | Oxygen index | The vertical combustion grade | The fusion drippage |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 | 70.0 64.6 61.4 70.8 65.5 67.3 | V-0 V-0 V-0 V-0 V-0 V-0 | Do not have |
From Fig. 1,2, especially Fig. 2 as can be seen, this polymkeric substance has the schlieren texture of nematic liquid crystal, the copolyesters that provable thus the present invention obtains is a liquid crystal liquid crystal property.Other embodiment observe under hot platform polarizing microscope, can observe the schlieren texture of nematic liquid crystal equally.
As can be seen from Table 1, the copolyesters that the present invention obtains not only has higher second-order transition temperature and 5% decomposition temperature, and the thermolysis residual volume at 650 ℃ all is higher than 30%, and it is good thermally-stabilised that this illustrates that it not only has, and has good one-tenth charcoal during burning.The fusing point of the copolyesters that obtains from the present invention has in addition reduced manyly than existing phosphorous liquid crystal copolyester, can mate with the processing temperature of most of thermoplastic resins fully.
From the data of table 2 as can be seen, the limiting oxygen index(LOI) of the copolyesters that the embodiment of the invention obtains is all greater than 60, and the vertical combustion grade all reached V-0, do not have the fusion drip phenomenon, shows all have excellent flame-retardant performance.
Claims (4)
1. liquid crystal atactic polyester containing phosphor is characterized in that this copolyesters is made up of the structural unit of following [I], [II], [III], [IV] expression:
Wherein the structural unit number of [I] accounts for 30～70% of all structural unit numbers, the structural unit number of [II]: structural unit number=0～9 of [IV]: 1, the structural unit number of { [II]+[IV] }: structural unit number=1～1.2 of [III]: 1, the segment of four kinds of structural units or its formation can be connected combination arbitrarily with hydroxy functional group by carboxyl, and the R in [III] formula represents that carbonatoms is 2～6 straight chained alkyl.
2. the preparation method of the described liquid crystal atactic polyester containing phosphor of claim 1; it is characterized in that this method is with following structure monomer; be acetylated P-hydroxybenzoic acid (A), terephthalic acid (B), terephthalic acid alkyl alcohol ester (C) and acetylated 9; the 10-dihydro-9-oxy is mixed-the assorted phenanthrene-Resorcinol (D) of 10-phosphinylidyne, is polymerized by melting state transesterification reaction:
R represents that carbonatoms is 2～6 straight chained alkyl in the formula, and concrete processing step is earlier starting monomer to be placed in the vacuum drying oven, dries by the fire 8～12 hours down in 60～100 ℃; Pressing monomer (A) again is all monomeric molar percentages 30～70%, the mol ratio of monomer (B) and monomer (C) is (B): (C)=0～9: 1, the mol ratio of the total amount of monomer (B) and monomer (C) and monomer (D) is (B+C): (D)=1～1.2: 1 proportioning weighing, and catalyzer is by being all starting monomer weight percent 0.01～0.1% weighings; Join in the reactor that has agitator with catalyzer then, feed nitrogen, under nitrogen protection, stirring heating heats up, and coreaction is 2～4.5 hours in 200～290 ℃ of temperature ranges; Stop logical nitrogen, begin then to vacuumize, and continue to heat up and in 270～320 ℃ of temperature ranges, continue reaction totally 0.5～2.5 hour, stop heating, be cooled to room temperature, promptly get the beige product.
3. according to the preparation method of the described liquid crystal atactic polyester containing phosphor of claim 2, it is characterized in that used catalyzer is selected from any in antimonous oxide, tetrabutyl titanate, four titanium oxide, manganese acetate, dialkyltin, the antimony glycol.
4. according to the preparation method of claim 2 or 3 described liquid crystal atactic polyester containing phosphors, it is characterized in that catalyzer is selected from any in antimonous oxide, tetrabutyl titanate, the antimony glycol.
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| CN102140164B (en) * | 2010-12-23 | 2012-10-31 | 大连工业大学 | Novel phosphorus and nitrogen containing flame-retardant thermotropic liquid crystal copolyester with low melting point and synthesis method thereof |
| KR101767690B1 (en) * | 2012-03-07 | 2017-08-11 | 심천 워트 어드밴스드 머티리얼즈 주식회사 | Composition for preparing thermosetting resin, cured product of the composition, prepreg having the cured product, and metal clad laminate and printed circuit board having the prepreg |
| CN112876663A (en) * | 2021-01-16 | 2021-06-01 | 赣州瑞德化工有限公司 | Preparation method of tin-based nano material modified polyester |
| CN113789053B (en) * | 2021-09-13 | 2023-04-25 | 宁夏清研高分子新材料有限公司 | High heat-resistant TLCP material and preparation method thereof |
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Assignee: Baosheng Science and Technology Innovation Co., Ltd. Assignor: Sichuan University Contract record no.: 2011320000540 Denomination of invention: Liquid crystal atactic polyester containing phosphor and its preparing method Granted publication date: 20080116 License type: Exclusive License Open date: 20060322 Record date: 20110408 |