CN101928385B - Liquid crystal polyester and preparation method thereof - Google Patents
Liquid crystal polyester and preparation method thereof Download PDFInfo
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- CN101928385B CN101928385B CN2009101081217A CN200910108121A CN101928385B CN 101928385 B CN101928385 B CN 101928385B CN 2009101081217 A CN2009101081217 A CN 2009101081217A CN 200910108121 A CN200910108121 A CN 200910108121A CN 101928385 B CN101928385 B CN 101928385B
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Abstract
The invention provides liquid crystal polyester. The polyester contains structural units shown in a formula 1, a formula 2, a formula 3 and a formula 4, wherein based on the total amount of the liquid crystal polyester, the content of a structural unit in the formula 4 is between 4 and 8 mole percent. The invention also provides a preparation method for the liquid crystal polyester. The melting point of the liquid crystal polyester is between 314 and 342 DEG C; and the tenacity and the rigidity of the liquid crystal polyester are high, so that the liquid crystal polyester is balanced and superior to various liquid crystal compositions in the prior art. Moreover, the preparation method for the liquid crystal polyester of the invention has the advantages of lowered equipment requirement and simple molding and processing.
Description
[technical field]
The present invention relates to the liquid crystal polyester field, relate in particular to the aromatic liquid-crystal polyester field.
[background technology]
Liquid crystalline polymers is a kind of novel high performance polymer material; Owing to its distinctive molecular structure has HS, high-modulus; Outstanding resistance toheat and superior corrosion resistance, flame retardant resistance and moulding processability have wide application prospect in the industrial production field.
The preparation of liquid crystalline polymers at present comes from mostly and has contraposition phenyl ring, 2,6-naphthalene nucleus and 4,4 '-monomer of structural units such as cyclohexyl biphenyl.This type liquid crystalline polymers has straight chain stiff molecule structure usually, can guarantee mechanical property and thermal property that liquid crystalline polymers is excellent, under melt temperature, has good flowability simultaneously.
But the toughness of the liquid crystalline polymers of being made up of rigid radical is relatively poor, has contradiction between the rigidity of the liquid crystalline polymers that promptly obtains and the toughness, makes the shock resistance of liquid crystalline polymers reduce.A kind of liquid-crystalline polyester composition is disclosed among the CN1727437A; Contain to benzene dioxy unit, right/a neighbour/benzene dicarbapentaborane unit, to oxygen phenylcarbamoyl unit, 2-hydroxyl-structural units such as 6-naphthoic acid; This liquid-crystalline polyester composition good moldability, planeness, flexural deformation, superior for heat resistance, but the toughness of said composition is relatively poor.
In addition, the fusing point of liquid crystalline polymers is too high usually, and processing units is had relatively high expectations, and is unfavorable for the forming process of polymkeric substance.US3637595 discloses one type and has used terephthalic acid, the liquid crystalline polymers of Resorcinol and PHB preparation, and its fusing point can not come forming process with the processing units of routine between 800-900F (426-483 ℃).
[summary of the invention]
The present invention exists contradiction, defective that fusing point is high in order to solve existing liquid-crystal compsn rigidity and toughness,
A kind of liquid crystal polyester is provided, contains the structural unit shown in following formula 1, formula 2, formula 3 and the formula 4,
Formula 1 formula 2
Formula 3 formulas 4
Wherein, be benchmark with the total amount of liquid crystal polyester, the content of the structural unit of formula 4 is 4-8 mole %.
The present invention also provides a kind of preparation method of liquid crystal polyester, comprises following steps: under the protection of inert gas that polymerisable monomer and catalyst mix is even, condensation reaction obtains said liquid crystal polyester; The monomer that contains following formula 5, formula 6, formula 7 and formula 8 in the polymerisable monomer;
Formula 5 formulas 6
Formula 7 formulas 8
Wherein, R
1-R
8Independently be H, C separately
1-C
3Alkyl or alkyl acyloxy; Total amount with polymerisable monomer is a benchmark, and the monomeric content of formula 8 is 4-8 mole %.
Liquid crystal polyester of the present invention, fusing point is 314-342 ℃, is lower than the various liquid crystal polyesters of prior art; In addition, the tensile strength of liquid crystal polyester of the present invention is 26.2-35.3MPa, and tensile modulus is 2.36-2.85GPa, and flexural strength is 33.7-42.6MPa, and modulus in flexure is 3.25-3.74GPa, and elongation at break is 3.1-6.6%.Among the preparation method of liquid crystal polyester of the present invention,, equipment requirements is reduced, so forming process is simple because the fusing point of said liquid crystal polyester is starkly lower than various liquid-crystal compsn of the prior art.
[embodiment]
The invention provides a kind of liquid crystal polyester, contain the structural unit shown in following formula 1, formula 2, formula 3 and the formula 4,
Formula 1 formula 2
Formula 3 formulas 4
Wherein, be benchmark with the total amount of liquid crystal polyester, the content of the structural unit of formula 4 is 4-8 mole %.
In liquid crystal polyester, draw the Si-O structure, and the internal rotation barrier potential of Si-O key is lower, thereby has destroyed this liquid crystal polyester molecule chain rigidity linear chain structure, cause the kindliness of molecular chain to increase, promptly strengthened the toughness of this liquid crystal polyester; Simultaneously, the regular degree of alignment between the molecular chain reduces, and can effectively reduce the fusing point of polymkeric substance; But the structural unit shown in the drawing-in system 4, promptly introduce the dimethyl silica structural unit after, polymer molecular chain becomes submissive by rigidity, has reduced the rigidity of liquid crystal polyester simultaneously at the flexible that strengthens liquid crystal polyester.Designer of the present invention finds through a large amount of experiments: the total amount with liquid crystal polyester is a benchmark, and when the content of the structural unit of formula 4 was 4-8 mole %, the rigidity of liquid crystalline polymers and toughness were all stronger, reach balance.
Among the present invention; Structural unit shown in the formula 1 is to oxygen phenylcarbamoyl structural unit; Structural unit shown in the formula 2 is to benzene dioxy structural unit, and the structural unit shown in the formula 3 is to benzene dicarbonyl structure unit, and formula 1, formula 2 and formula 3 are as the rigid structure unit in the liquid crystal polyester; Structural unit shown in the formula 4 is the dimethyl silica structural unit, as the flexible structure unit in the liquid crystal polyester.
Among the present invention, keeping liquid crystal polyester to have than lower melting point, better under the flexible prerequisite, thermotolerance also is improved simultaneously, is benchmark with the total amount of liquid crystal polyester, and the content of the structural unit of formula 1 is 20-60 mole %, is preferably 40-50 mole %; The content of the structural unit of formula 2 is 12-36 mole %, is preferably 22-26 mole %; The content of the structural unit of formula 3 is 20-40 mole %, is preferably 25-35 mole %.
According to liquid crystal polyester provided by the invention, consider that this liquid crystal polyester can provide mechanical property and thermal property preferably, the weight-average molecular weight of said liquid crystal polyester is 10000-25000, is preferably 20000-25000.
Liquid crystal polyester of the present invention contains the structural unit shown in the above-mentioned formula 1-4, and structural unit shown in the formula 4 accounts for the 4-8 mole % of liquid crystal polyester total amount; Make that the fusing point of this liquid crystal polyester is 314-342 ℃; Tensile strength is 26.2-35.3MPa, and tensile modulus is 2.36-2.85GPa, and flexural strength is 33.7-42.6MPa; Modulus in flexure is 3.25-3.74GPa, and elongation at break is 3.1-6.6%.
The present invention also provides a kind of preparation method of liquid crystal polyester, comprises following steps: under the protection of inert gas that polymerisable monomer and catalyst mix is even, condensation reaction obtains said liquid crystal polyester; The monomer that contains following formula 5, formula 6, formula 7 and formula 8 in the polymerisable monomer;
Formula 5 formulas 6
Formula 7 formulas 8
Wherein, R
1-R
8Independently be H, C separately
1-C
3Alkyl or alkyl acyloxy; Total amount with polymerisable monomer is a benchmark, and the monomeric content of formula 8 is 4-8 mole %.
Among the present invention; Catalyzer exists down; Make the polymerisable monomer that contains formula 5, formula 6, formula 7 and formula 8 under high temperature fused state; The transesterify condensation reaction takes place, and obtains having to oxygen phenylcarbamoyl structural unit, to benzene dioxy structural unit, to the liquid crystal polyester of benzene dicarbonyl structure unit and dimethyl silica structural unit; Pass through the monomeric add-on of control polymerisable monomer Chinese style 8 simultaneously, thus the content of the dimethyl silica structural unit in the liquid crystal polyester that control obtains at last, thus realize that preparation has relatively low fusing point, better flexible liquid crystal polyester.
The various catalyzer that said catalyzer is used always for those skilled in the art.Total amount with polymerisable monomer is a benchmark, and the content of catalyzer is 0.1-1 mole %.Among the present invention, said catalyzer preferably adopts sodium acetate.
Setting rate when delaying to cool off for appropriateness; Make liquid crystal polyester of the present invention improve thermotolerance, and the crystalline state of liquid crystal polyester to control to the best when discharging in the polymeric kettle; Among the present invention; Total amount with polymerisable monomer is a benchmark, and the monomeric content of formula 5 is 20-60 mole %, is preferably 40-50 mole %; The monomeric content of formula 6 is 12-36 mole %, is preferably 22-26 mole %; The monomeric content of formula 7 is 20-40 mole %, is preferably 25-35 mole %.
As a kind of preferred implementation of the present invention, for guaranteeing that polymerisable monomer can react completely, in the polymerisable monomer according to the invention, formula 6 equates with the monomeric molar content of formula 7 with the monomeric mole total amount of formula 8.
Preparation in accordance with the present invention along with the carrying out of condensation reaction, can produce a large amount of by product carboxylic acids, makes the viscosity of reaction system also become big gradually, can hinder the carrying out of reaction.Therefore among the preparation method provided by the invention, reaction needs is carried out under protection of inert gas, through rare gas element the by product carboxylic acid is brought out from reaction system under the high temperature.The various rare gas elementes that said rare gas element is used always for those skilled in the art, for example nitrogen, argon gas.
Among the present invention, be solid under the monomer normal temperature of formula 5-formula 8, so condensation reaction must be carried out under high temperature fused state.The temperature of condensation reaction is 150-330 ℃, and the time of condensation reaction is 10-15h.In the condensation reaction of the present invention, the preferred method that adopts temperature programming that heats up, more preferably: be warming up to 150 ℃ in the 50-60min, insulation 120min; Be warming up to 240 ℃ then in the 30-40min, insulation 45min; In 20min, be warming up to 280 ℃, insulation 45min; Be warming up to 290 ℃ in the 5min, insulation 1h; In 10min, be warming up to 300 ℃ then, insulation 2h; In 10min, be warming up to 320 ℃, insulation 1h; In 10min, be warming up to 330 ℃, insulation 45min; Apply rough vacuum (10mmHg) 50min.
As a kind of preferred implementation of the present invention; Monomer shown in the said formula 5 adopts acetoxy-benzoic acid; Monomer shown in the formula 6 adopts the hydroquinone diaeetate, and the monomer shown in the formula 7 adopts terephthalic acid, and the monomer shown in the formula 8 adopts dimethyl-diacetoxy silane; Condensation reaction takes place down in 150-330 ℃ of nitrogen protection, and catalyzer is a sodium acetate.Adopt the preferred embodiment of the present invention, used monomer is with low cost, and the preparation method is simple, and is lower to equipment requirements, and the production rate of liquid crystal polyester is higher.
Through embodiment the present invention is further described below.Raw materials usedly in embodiment and the Comparative Examples all be commercially available.
Embodiment 1
4-acetoxy-benzoic acid (formula 5) with 360.1g (40 moles of %); Hydroquinone diaeetate's (formula 6) of (252.5g 26 moles of %); 249.0g the terephthalic acid (formula 7) of (30 moles of %) in the reaction kettle of the anhydrous sodium acetate impouring 1L of the dimethyl-diacetoxy silane (formula 8) of 35.2g (4 moles of %) and 2.9g (0.7 mole of %), vacuumizes; Charge into nitrogen then, carry out so repeatedly three times.Under nitrogen atmosphere, within 1h, temperature is increased to 150 ℃, insulation 2h is increased to 240 ℃ with temperature in 30min; Insulation 45min is warming up to 280 ℃ in 20min, insulation 45min; Be warming up to 290 ℃ in the 5min, insulation 1h is warming up to 300 ℃ in the 10min; Insulation 2h is warming up to 320 ℃ at last in 10min, insulation 1h; Be warming up to 330 ℃, insulation 45min also applies rough vacuum (10mmHg) and reaches 50min under this temperature, when moment of torsion reaches peak under the stirring velocity at 20rpm, stops heating and vacuumizes.Through aforesaid method, obtain liquid crystal polyester of the present invention, be designated as A1.
Embodiment 2
Present embodiment adopts and prepares liquid crystal polyester of the present invention with embodiment 1 identical method, and difference is that polymerisable monomer is:
| Monomer | Kind | Consumption |
| Formula 5 | The 4-acetoxy-benzoic acid | (396.1g 44 moles of %) |
| Formula 6 | The hydroquinone diaeetate | (223.4g 23 moles of %) |
| Formula 7 | Terephthalic acid | (232.4g 28 moles of %) |
| Formula 8 | Dimethyl-diacetoxy silane | (44.1g 5 moles of %) |
Through aforesaid method, obtain liquid crystal polyester of the present invention, be designated as A2.
Embodiment 3
Present embodiment adopts and prepares liquid crystal polyester of the present invention with embodiment 1 identical method, and difference is that polymerisable monomer is:
| Monomer | Kind | Consumption |
| Formula 5 | The 4-acetoxy-benzoic acid | (360.1g 40 moles of %) |
| Formula 6 | Resorcinol | (121.0g 22 moles of %) |
| Formula 7 | Terephthalic acid | (249.0g 30 moles of %) |
| Formula 8 | Dimethyl-diacetoxy silane | (70.5g 8 moles of %) |
Through aforesaid method, obtain liquid crystal polyester of the present invention, be designated as A3.
Embodiment 4
Present embodiment adopts and prepares liquid crystal polyester of the present invention with embodiment 1 identical method, and difference is that polymerisable monomer is:
| Monomer | Kind | Consumption |
| Formula 5 | The 4-acetoxy-benzoic acid | (315.1g 36 moles of %) |
| Formula 6 | The hydroquinone diaeetate | (340.0g 26 moles of %) |
| Formula 7 | Terephthalic acid | (258.2g 32 moles of %) |
| Formula 8 | Dimethyl-acetoxyl group propionyloxy silane | (55.5g 6 moles of %) |
Through aforesaid method, obtain liquid crystal polyester of the present invention, be designated as A4.
Embodiment 5
Present embodiment adopts and prepares liquid crystal polyester of the present invention with embodiment 1 identical method, and difference is that polymerisable monomer is:
| Monomer | Kind | Consumption |
| Formula 5 | 4-propionyloxy phenylformic acid | (504.4g 56 moles of %) |
| Formula 6 | The Resorcinol dipropionate | (166.5g 15 moles of %) |
| Formula 7 | Terephthalic acid | (182.6g 22 moles of %) |
| Formula 8 | Dimethyl-diacetoxy silane | (61.7g 7 moles of %) |
Through aforesaid method, obtain liquid crystal polyester of the present invention, be designated as A5.
Comparative Examples 1
This Comparative Examples adopts and prepares liquid crystal polyester of the present invention with embodiment 1 identical method, and difference is that polymerisable monomer is:
| Monomer | Kind | Consumption |
| Formula 5 | The 4-acetoxy-benzoic acid | (360.1g 40 moles of %) |
| Formula 6 | The hydroquinone diaeetate | (262.2g 27 moles of %) |
| Formula 7 | Terephthalic acid | (249.0g 30 moles of %) |
| Formula 8 | Dimethyl-diacetoxy silane | (26.4g 3 moles of %) |
Preparation is designated as D1 according to the preparation process institute synthetic liquid crystal polyester among the embodiment.
Comparative Examples 2
This Comparative Examples adopts and prepares liquid crystal polyester of the present invention with embodiment 1 identical method, and difference is that polymerisable monomer is:
| Monomer | Kind | Consumption |
| Formula 5 | The 4-acetoxy-benzoic acid | (360.1g 40 moles of %) |
| Formula 6 | The hydroquinone diaeetate | (203.9g 21 moles of %) |
| Formula 7 | Terephthalic acid | (249.0g 30 moles of %) |
| Formula 8 | Dimethyl-diacetoxy silane | (79.3g 9 moles of %) |
Through aforesaid method, obtain liquid crystal polyester, be designated as D2.
Comparative Examples 3
This Comparative Examples adopts and prepares liquid crystal polyester of the present invention with embodiment 1 identical method, and difference is that polymerisable monomer is:
| Kind | Consumption |
| 2-hydroxyl-6-naphthoic acid | (376.4g 40 moles of %) |
| Terephthalic acid | (207.5g 25 moles of %) |
| 4,4 '-dihydroxybiphenyl | (232.8g 25 moles of %) |
| The 4-hydroxy-benzoic acid | (69.1g 10 moles of %) |
Through aforesaid method, obtain liquid crystal polyester, be designated as D3.
Performance test:
With the liquid crystal polyester product of embodiment 1-5 and Comparative Examples 1-3 preparation test specimen, carry out following test respectively through forcing machine extruding pelletization and injection moulding corresponding size.
(1) pass through ASTM method D638 measures each test specimen under the elongation of 50mm/min tensile strength and elongation at break, test result is as shown in table 1.
(2) pass through ASTM method D790 measures each test specimen under 1.3mm/min speed flexural strength, test result is as shown in table 1.
(3) fusing point through each test specimen of dsc measurement, 20 ℃/min of temperature rise rate, 10 ℃/min of rate of temperature fall.
Table 1
| Sample | Fusing point (℃) | Tensile strength (MPa) | Tensile modulus (GPa) | Flexural strength (MPa) | Modulus in flexure (GPa) | Elongation at break (%) |
| A1 | 342 | 35.3 | 2.85 | 42.6 | 3.74 | 3.1 |
| A2 | 336 | 32.7 | 2.69 | 38.8 | 3.65 | 3.9 |
| A3 | 314 | 26.2 | 2.36 | 33.7 | 3.25 | 6.6 |
| A4 | 329 | 29.3 | 2.56 | 36.4 | 3.50 | 4.7 |
| A5 | 320 | 27.6 | 2.44 | 34.2 | 3.35 | 5.8 |
| D1 | 351 | 39.5 | 3.32 | 47.4 | 4.11 | 1.9 |
| D2 | 303 | 23.6 | 2.15 | 30.9 | 3.04 | 7.7 |
| D3 | 358 | 41.3 | 4.07 | 46.7 | 4.71 | 1.2 |
Result by A1-A5 and D1-D3 in the last table 1 relatively can find out; Contain the dimethyl silica structural unit in the liquid crystal polyester provided by the present invention; And when the molar content of dimethyl silica structural unit is 4-8%, the fusing point of liquid crystal polyester lower (314-342 ℃), elongation at break is 3.1-6.6%; Flexural strength is 33.7-42.6MPa; Tensile strength is 26.2-35.3MPa, and promptly the toughness of liquid crystal polyester and rigidity are all stronger, and various liquid crystalline polymers toughness that obtain among the D1-D3 and rigidity can not reach higher simultaneously.
Claims (6)
1. liquid crystal polyester contains the structural unit shown in following formula 1, formula 2, formula 3 and the formula 4,
Formula 1 formula 2
Formula 3 formulas 4
Wherein, be benchmark with the total amount of liquid crystal polyester, the content of the structural unit of formula 4 is 4-8 mole %, and the content of the structural unit of formula 1 is 20-60 mole %, and the content of the structural unit of formula 2 is 12-36 mole %, and the content of the structural unit of formula 3 is 20-40 mole %; The weight-average molecular weight of said liquid crystal polyester is 10000-25000.
2. liquid crystal polyester according to claim 1; It is characterized in that the fusing point of said liquid crystal polyester is 314 ℃-342 ℃, tensile strength is 26.2-35.3MPa; Tensile modulus is 2.36-2.85GPa; Flexural strength is 33.7-42.6MPa, and modulus in flexure is 3.25-3.74GPa, and elongation at break is 3.1-6.6%.
3. the preparation method of the described liquid crystal polyester of claim 1, comprise following steps: under the protection of inert gas that polymerisable monomer and catalyst mix is even, condensation reaction obtains said liquid crystal polyester; The monomer that contains following formula 5, formula 6, formula 7 and formula 8 in the polymerisable monomer;
Formula 5 formulas 6
Formula 7 formulas 8
Wherein, R
1-R
8Independently be H, C separately
1-C
3Alkyl or alkyl acyloxy; Total amount with polymerisable monomer is a benchmark, and the monomeric content of formula 8 is 4-8 mole %, and the monomeric content of formula 5 is 20-60 mole %, and the monomeric content of formula 6 is 12-36 mole %, and the monomeric content of formula 7 is 20-40 mole %.
4. method according to claim 3 is characterized in that, is benchmark with the total amount of polymerisable monomer, and the content of catalyzer is 0.1-1 mole %.
5. according to claim 3 or 4 described methods, it is characterized in that said catalyzer is a sodium acetate.
6. method according to claim 3 is characterized in that, the temperature of reaction of said condensation reaction is 150-330 ℃, and the time of condensation reaction is 10-15h.
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| CN2009101081217A CN101928385B (en) | 2009-06-22 | 2009-06-22 | Liquid crystal polyester and preparation method thereof |
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| CN2009101081217A CN101928385B (en) | 2009-06-22 | 2009-06-22 | Liquid crystal polyester and preparation method thereof |
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| CN101928385B true CN101928385B (en) | 2012-06-20 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3637595A (en) * | 1969-05-28 | 1972-01-25 | Steve G Cottis | P-oxybenzoyl copolyesters |
| EP0745634A1 (en) * | 1995-05-30 | 1996-12-04 | General Electric Company | Method for making poly(arylsiloxane)compositions |
| CN1727437A (en) * | 2004-07-30 | 2006-02-01 | 汎塑料株式会社 | Liquid crystalline polyester resin composition |
| CN1820034A (en) * | 2002-10-15 | 2006-08-16 | 埃克森美孚化学专利公司 | Polyolefin adhesive compositions and articles made therefrom |
-
2009
- 2009-06-22 CN CN2009101081217A patent/CN101928385B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3637595A (en) * | 1969-05-28 | 1972-01-25 | Steve G Cottis | P-oxybenzoyl copolyesters |
| EP0745634A1 (en) * | 1995-05-30 | 1996-12-04 | General Electric Company | Method for making poly(arylsiloxane)compositions |
| CN1820034A (en) * | 2002-10-15 | 2006-08-16 | 埃克森美孚化学专利公司 | Polyolefin adhesive compositions and articles made therefrom |
| CN1727437A (en) * | 2004-07-30 | 2006-02-01 | 汎塑料株式会社 | Liquid crystalline polyester resin composition |
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