CN103665354B - The application of a kind of liquid crystal polyester, its preparation method, its composition and composition thereof - Google Patents
The application of a kind of liquid crystal polyester, its preparation method, its composition and composition thereof Download PDFInfo
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- CN103665354B CN103665354B CN201210328681.5A CN201210328681A CN103665354B CN 103665354 B CN103665354 B CN 103665354B CN 201210328681 A CN201210328681 A CN 201210328681A CN 103665354 B CN103665354 B CN 103665354B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
Abstract
The invention discloses the application of a kind of liquid crystal polyester, its preparation method, its composition and composition thereof.A kind of liquid crystal polyester, comprises formula I, the repeating unit shown in (II) and (III):
,-O-Ar
1-O-(II) ,-OC-Ar
2-CO-(III).Preparation method described in liquid crystal polyester of the present invention comprises molten prepolymer polymerization and solid state polymerization two steps.The Tc of gained liquid crystal polyester and the difference of heat-drawn wire are 10-20 DEG C, are conducive to the processing characteristics that liquid crystal polyester does not lose again its excellence while keeping its use temperature.In addition the composition that prepared by liquid crystal polyester of the present invention and mineral filler has excellent shock resistance and that resist warping deformation performance, can be widely used in field of electronics.
Description
Technical field
The present invention relates to field of polymer technology, particularly a kind of liquid crystal polyester, its preparation method and comprise composition and the application thereof of this liquid crystal polyester.
Background technology
Liquid crystal polyester (LCP) has excellent thermotolerance, from flame retardant resistance, dimensional stability, electrical property and processing fluidity, in field widespread uses such as electronic apparatuss.Along with miniaturization, the thin-walled property of electronic apparatus product, facilitate the development of electronic component densification, microminiaturization and high density packaging technique, require also to improve constantly to the temperature tolerance of LCP material used.Particularly adopt surface mounting technique (SurfaceMountTechnology is called for short SMT), and lead-free scolding tin is generally used, and has higher requirement to the temperature tolerance of LCP material used.For same material, usually need it both to have good processing characteristics, its use temperature can not be too low simultaneously.Heat-drawn wire (HDT) weighs the important parameter of of polymkeric substance use temperature, and when melt temperature one timing of LCP, when the difference of Tc and HDT exceedes certain limit, its HDT is less than normal, then its Applicable temperature is lower; And when the difference of Tc and HDT is less, the difference of its melt temperature and Tc will certainly be comparatively large, this situation can make material in molding process, cooling curing time lengthening and reduce mould efficiency.Therefore the difference of Tc and HDT must be limited within certain temperature range.
When LCP is used in the mouldings of thin-walled property, even if having the advantage of good fluidity to a certain extent, but require higher thin wall parts in recent years, higher requirement be it is also proposed to the shock resistance of material and that resist warping performance.
Summary of the invention
In view of the above, the present invention is necessary to provide a kind of liquid crystal polyester.
Further, the preparation method that a kind of liquid crystal polyester is provided is necessary.
Further, the composition that a kind of liquid crystal polyester is provided is necessary.
Further, the application of the composition that a kind of liquid crystal polyester is provided is necessary.
The technical solution adopted in the present invention is, a kind of liquid crystal polyester, comprises formula I, (II), the repeating unit shown in (III):
——O——Ar
1——O——（Ⅱ）、
——OC——Ar
2——CO——（Ⅲ），
Wherein, Ar
1be selected from
Ar
2comprise
The molar ratio of the repeating unit shown in formula I is 55-65%, based on whole repeating units of described liquid crystal polyester;
The molar ratio of the repeating unit shown in formula II is 17.5-22.5%, based on whole repeating units of described liquid crystal polyester;
The molar ratio of the repeating unit shown in formula III is 17.5-22.5%, based on whole repeating units of described liquid crystal polyester.
Wherein, the molar weight of the repeating unit shown in the molar weight of the repeating unit shown in formula III and formula II is in a ratio of 0.9-1.1.
A kind of liquid crystal polyester, its repeating unit only comprises and being made up of the repeating unit shown in formula I, (II), (III):
——O——Ar
1——O——（Ⅱ）、
——OC——Ar
2——CO——（Ⅲ），
Wherein, Ar
1comprise
Ar
2comprise
and it is optional
The molar ratio of the repeating unit shown in formula I is 55-65%, based on whole repeating units of described liquid crystal polyester;
The molar ratio of the repeating unit shown in formula II is 17.5-22.5%, based on whole repeating units of described liquid crystal polyester;
The molar weight of the repeating unit shown in the molar weight of the repeating unit shown in formula III and formula II is in a ratio of 0.9-1.1.
Wherein, the repeating unit shown in described (II) comprises
repeating unit shown in its Chinese style (b) Yu formula (a) mole ratio be 0-1.
Wherein, the repeating unit shown in described (III) comprises
Wherein, molar weight c, d and e of the repeating unit shown in (c), (d) He (e) meet following relationship: 0 < e/ [c+d+e]≤29%.
Molar weight c, d and e of the repeating unit shown in described (c), (d) He (e) meet following relationship: 11.1%≤e/ [c+d+e]≤28.6%.
Wherein the value of e/ [c+d+e] also can be 12.5%, 17.7%, 25%.
Wherein, described liquid crystal polyester is made up of the repeating unit shown in formula I, (a) and (b), (c), (d) He (e).
Wherein, described liquid crystal polyester is 300-360 DEG C by the melt temperature that differential scanning calorimeter is determined.
Wherein, described liquid crystal polyester measures heat-drawn wire for 245-305 DEG C with the heating rate of 2 DEG C/min according to ISO75-2 standard under 1.82MPa load.
Wherein, the Tc of described liquid crystal polyester and the difference of heat-drawn wire are 10-20 DEG C, and preferred scheme can reach 11-18 DEG C.
A kind of preparation method of above-mentioned liquid crystal polyester:
In proportion by monomer
with optional
put in reactor, under acetic anhydride acylating agent and catalyst action, melt polymerization prepares prepolymer, then carries out solid state polymerization and prepares liquid crystal polyester.
The repeating unit (I) of above-mentioned liquid crystal polyester, (a) and (b), (c), (d) with the monomer of (e) correspondence are respectively
with optional
In the present invention, pre-polymerization process adds the acylating agent of diacetyl oxide as hydroxyl in monomer, and its consumption is 1-1.5 times of monomer hydroxyl mole number, and preferred 1.02-1.2 doubly.
Can use various catalyzer in polymerization, the representative example of catalyzer comprises dialkyl tin oxide, diaryltin oxide compound, titan-alkoxide class, alkali and alkaline-earth metal salt and BF
3and so on lewis acid, wherein the acetate of catalyzer preferred Zn, K, Mg, Ca or Co or fragrant hydrochlorate are catalyzer, and the consumption of catalyzer is based on the 0.001-1% of total monomer weight, preferred 0.05-0.2%.
The reaction conditions of polymerization is, 120-150 DEG C of acetylize 1-6 hour, then with the ramp of 10-60 DEG C/h to this prepolymer melt temperature above 0-25 DEG C (prepolymerization maximum temperature), and insulation reaction 10 minutes to 4 hours; The pressure of end reaction system is 133-101080Pa, is preferably 133-6670Pa.
The prepolymer of the molten state prepared by above polymerization process, is discharged by reaction container bottom under the impressed pressure of 0.05-0.6MPa, is processed to the form of columnar structure particle, spherical or ellipticity particle.Wherein the cross-sectional area of columnar structure particle is 7-24mm
2, length is 3-6mm; Spherical or ellipticity particle volume is 15-65mm
3.
Wherein, the prepolymer prepared by aforesaid method higher than its melt temperature 10 DEG C, 1000s
-1be 4-8Pa.s by the melt viscosity of capillary rheometer determining under shearing rate.
The particulate state prepolymer manufactured by above-mentioned polymerization process can heat the liquid crystal polyester that solid state polymerization obtains expection viscosity further in decompression or rare gas element, the optimum condition of solid state polymerization is that temperature of reaction is at 10-80 DEG C below prepolymer melt temperature, temperature of reaction is 20-60 DEG C below melt temperature preferably, pressure≤1000Pa, preferred pressure≤200Pa; Reaction times is 1-24 hour.
Wherein, the prepolymer prepared by aforesaid method higher than its melt temperature 20 DEG C, 1000s
-1be 15-100Pa.s by the melt viscosity of capillary rheometer determining under shearing rate, preferred 20-50Pa.s.
Invention further provides the composition comprising above-mentioned liquid-crystal polyester resin, the liquid-crystalline polyester composition obtained by adding one or more additives can be used for multiple field.
The composition of a kind of liquid crystal polyester provided by the invention, comprises liquid crystal polyester from the above mentioned and mineral filler.
The additive that can mix with liquid-crystal polyester resin comprises mineral filler and/or strongthener, and described mineral filler or strongthener can be threadiness, sheet or granular.
Bat wool and/or strongthener comprise the one or more combination in glass fibre, sapphire whisker, carbon fiber, potassium titanate fiber, boric acid fibre, wollastonite fibre, preferred glass fibers; Wherein the cross section of fiber can be one in circular cross section, elliptic cross-section, rectangular cross section or optional combination.
It is one or more combination in glass flake, mica, glass microballon, talcum powder, clay, graphite, calcium carbonate, barium sulfate, titanium dioxide that described sheet and/or granular mineral filler comprise.
The composition of this liquid crystal polyester, comprises the above-mentioned liquid crystal polyester of 100 weight parts and the mineral filler of 1-200 weight part and/or strongthener.
The composition of above-mentioned liquid crystal polyester is applied to field of electronics.
The Tc of liquid crystal polyester of the present invention and the difference of heat-drawn wire are 10-20 DEG C, and preferred scheme is 11-18 DEG C, and the molding cycle that liquid crystal polyester adds man-hour is shorter.
In addition, composition prepared by liquid crystal polyester of the present invention and other mineral filler, its that resist warping performance is also lower, be convenient to application, and its shock resistance is better.
Embodiment
Be described further below in conjunction with the application of some embodiments to liquid crystal polyester of the present invention, its preparation method, its composition and composition thereof.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
Object of the present invention is intended to a kind of liquid crystal polyester, and the difference of its Tc and heat-drawn wire is 10-20 DEG C, and preferred scheme can reach 11-18 DEG C, and the molding cycle that liquid crystal polyester adds man-hour can reduce.The composition prepared by this liquid crystal polyester and other filler, it is excellent in cushion effect and buckling deformation is low, is convenient to be applied in electronic apparatus thin wall parts field.
The buckling deformation measuring method of liquid-crystalline polyester composition of the present invention is as follows:
The melt temperature of described liquid crystal polyester and Tc are measured by the resistance to DSC200F3 that speeds, at 40mL/min nitrogen atmosphere, under, sample is heated to 400 DEG C from room temperature with the temperature rise rate of 20 DEG C/min and keeps 2min, again sample is cooled to room temperature with the rate of temperature fall of 20 DEG C/min, record exothermic peak (Tc) is Tc; And then sample is heated to 400 DEG C with the temperature rise rate of 20 DEG C/min, the endotherm(ic)peak recorded on this heating curve is melt temperature (Tm).
Wherein, the testing method of heat-drawn wire is as follows, is the sample of 80mm × 10mm × 4mm by liquid-crystal polyester resin injection moulding, uses this sample under 1.82MPa load, to measure heat-drawn wire according to ISO75-2 standard with the heating rate of 2 DEG C/min.
Be 100mm by liquid-crystalline polyester composition injection moulding diameter, thickness is the plectane of 1.5mm.Plectane is placed in horizontal table top, measure the surperficial distance between desktop of plectane, choose two distance maximum point (A, B) and two smallest point (C, D), buckling deformation (w) is calculated as follows: w=(A+B)/2-(C+D)/2, w values are less, represent that resist warping performance of test strip is better.
Melt viscosity: adopt DyniscoLCR7001 type capillary rheometer to test, port mould diameter is 1mm, and length is 20mm, prepolymer more than its melt temperature 10 DEG C, liquid crystal polyester more than its melt temperature 20 DEG C, shearing rate is 1000s
-1viscosity under condition is melt viscosity.
Notched Izod impact strength: Izod breach is tested according to ISO180 standard.
In embodiment below and comparative example, use the structure of monomer and abbreviation as follows respectively:
p-hydroxybenzoic acid (HBA);
'-biphenyl diphenol (BP);
resorcinol (HQ);
terephthalic acid (TPA);
m-phthalic acid (IPA);
nDA (NDA);
acetic anhydride (AA).
Above material all can on the market buy obtain.
Embodiment 1
The preparation of liquid crystal polyester
Be furnished with nitrogen inlet, be with in 100 liters of reactors of agitator of power of agitator display, add 15.19kg (110mol) HBA, 6.517kg (35mol) BP, 1.1kg (10mol) HQ, 3.32kg (20mol) TPA, 2.824kg (17mol) IPA, 1.73kg (8mol) NDA, 21.44kg (210mol) AA and 3.07g magnesium acetate.After displacement nitrogen, back flow reaction 3 hours under nitrogen atmosphere temperature of reaction being elevated to 145 DEG C; Afterwards with 60 DEG C/h of ramp to 315 DEG C (prepolymerization maximum temperature), keep reacting after 30 minutes at such a temperature, in 30min, be evacuated to 200Pa continuation reaction reach preset value to power of agitator.Then being 0.2MPa by adding nitrogen to pressure in reactor, being discharged by still bottom valve, being cut into cross-sectional diameter with dicing machine after crossing tank is 16mm
2, length is the prepolyer granule of 5mm.
Above-mentioned for 10kg prepolyer granule is added 50 liters with in the reactor of agitator, then at 250 DEG C, vacuum tightness is that under 25Pa condition, solid state polycondensation obtains final liquid crystal polyester in 5 hours.
The melt temperature of gained liquid crystal polyester, Tc, the test result of heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
The liquid crystal polyester 60 weight parts of gained being prepared by aforesaid method joins forcing machine from twin-screw extrusion owner spout, 25 parts of glass fibre and 15 parts of sheet mica is joined forcing machine from twin-screw extrusion pusher side spout.Melting mixing under the screw speed of 300RPM, barrel temperature is 270-305 DEG C, extrudes the composition obtaining liquid crystal polyester, respectively test composition that resist warping performance and resistance to impact shock, and its test result is listed in table 2.
Embodiment 2
The preparation of liquid crystal polyester
By 15.19kg (110mol) HBA, 6.517kg (35mol) BP, 1.1kg (10mol) HQ, 4.98kg (30mol) TPA, 0.83kg (5mol) IPA, 2.16kg (10mol) NDA, 21.44kg (210mol) AA and 3.08g magnesium acetate with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 280-315 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Embodiment 3
The preparation of liquid crystal polyester
By 15.19kg (110mol) HBA, 7.45kg(40mol) BP, 0.55kg(5mol) HQ, 4.98kg(30mol) TPA, 1.66kg(10mol) IPA, 1.08kg(5mol) NDA, 21.44kg(210mol) AA and 3.09g magnesium acetate with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to the method for embodiment 1, except barrel temperature is 300-345 DEG C of condition, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Comparative example 1
The preparation of liquid crystal polyester
By 15.19kg (110mol) HBA, 6.52kg(35mol) BP, 1.1kg(10mol) HQ, 4.98kg(30mol) TPA, 2.49kg(15mol) IPA, 21.44kg(210mol) AA and 3.03g magnesium acetate is with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 310-360 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Embodiment 4
The preparation of liquid crystal polyester
By 16.58kg (120mol) HBA, 3.72kg(20mol) BP, 2.2kg(20mol) HQ, 3.32kg(20mol) TPA, 1.66kg(10mol) IPA, 2.16kg(10mol) NDA, 21.44kg(210mol) AA and 2.96g magnesium acetate with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 260-305 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Embodiment 5
The preparation of liquid crystal polyester
By 16.58kg (120mol) HBA, 3.72kg(20mol) BP, 2.2kg(20mol) HQ, 4.98kg(30mol) TPA, 0.83kg(5mol) IPA, 1.08kg(5mol) NDA, 21.44kg(210mol) AA and 2.94g magnesium acetate with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 290-335 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Embodiment 6
The preparation of liquid crystal polyester
By 16.58kg (120mol) HBA, 5.59kg(30mol) BP, 1.1kg(10mol) HQ, 3.32kg(20mol) TPA,, 1.66kg(10mol) and IPA, 2.16kg(10mol) NDA, 21.44kg(210mol) AA and 3.04g magnesium acetate is with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 270-305 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Embodiment 7
The preparation of liquid crystal polyester
By 16.58kg (120mol) HBA, 5.59kg(30mol) BP, 1.1kg(10mol) HQ, 4.98kg(30mol) TPA, 0.83kg(5mol) IPA, 1.08kg(5mol) NDA, 21.44kg(210mol) AA and 3.02g magnesium acetate with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 305-345 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Comparative example 2
The preparation of liquid crystal polyester
By 16.58kg (120mol) HBA, 3.72kg(20mol) BP, 2.2kg(20mol) HQ, 4.98kg(30mol) TPA, 1.66kg(10mol) IPA, 21.44kg(210mol) AA and 2.92g magnesium acetate is with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 300-335 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Comparative example 3
The preparation of liquid crystal polyester
By 16.58kg (120mol) HBA, 7.45kg(40mol) BP, 4.98kg(30mol) TPA, 1.66kg(10mol) IPA, 21.44kg(210mol) AA and 3.07g magnesium acetate is with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 310-355 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Embodiment 8
The preparation of liquid crystal polyester
By 17.96kg (130mol) HBA, 4.66kg(25mol) BP, 1.1kg(10mol) HQ, 3.32kg(20mol) TPA, 1.66kg(10mol) IPA, 1.08kg(5mol) NDA, 21.44kg(210mol) AA and 2.98g magnesium acetate with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 280-315 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Embodiment 9
The preparation of liquid crystal polyester
By 17.96kg (130mol) HBA, 6.52kg(35mol) BP, 3.32kg(20mol) TPA, 0.83kg(5mol) IPA, 2.16kg(10mol) NDA, 21.44kg(210mol) AA and 3.08g magnesium acetate is with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 270-305 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Embodiment 10
The preparation of liquid crystal polyester
By 17.96kg (130mol) HBA, 6.52kg(35mol) BP, 4.15kg(25mol) TPA, 0.83kg(5mol) IPA, 1.08kg(5mol) NDA, 21.44kg(210mol) AA and 3.05g magnesium acetate is with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 290-325 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
Comparative example 4
The preparation of liquid crystal polyester
By 17.96kg (130mol) HBA, 6.52kg(35mol) BP, 4.32kg(26mol) TPA, 1.5kg(9mol) IPA, 21.44kg(210mol) AA and 3.03g magnesium acetate is with reference to embodiment 1 method, except the temperature of the highest polymerization temperature of prepolymerization, solid state polymerization in such as table 1, vacuum tightness and time prepare liquid crystal polyester.
The melt temperature of the cross-sectional area of gained liquid crystal polyester prepolymer, prepolymer melt viscosity and liquid crystal polyester, Tc, the test result such as heat-drawn wire, melt viscosity lists in table 1.
The preparation of liquid-crystalline polyester composition
With reference to method and the weight part of embodiment 1, except barrel temperature is 300-335 DEG C, prepare the composition of liquid crystal polyester, composition that resist warping performance and resistance to impact shock, its test result is listed in table 2.
The polymerization parameter of table 1 liquid crystal polyester and physicals
Table 2 liquid-crystalline polyester composition performance
Associative list 1 and table 2, by the liquid crystal polyester that technical scheme disclosed in this invention prepares, its heat-drawn wire is between 250-305 DEG C, and the difference of its Tc and heat-drawn wire is between 10-20 DEG C of scope, in comparative example, the Tc of liquid crystal polyester and the difference of heat-drawn wire are greater than 20 DEG C or be less than 10 DEG C, liquid crystal polyester of the present invention, the difference of its Tc and heat-drawn wire is between 10-20 DEG C of scope, the Tc of liquid crystal polyester and the difference of HDT effectively control within certain temperature range, material cooling curing time lengthening and reduce mould efficiency in molding process can not be made, have simultaneously and do not lose its resistance to elevated temperatures.
By the contrast one by one of embodiment and comparative example, can find, in liquid crystal polyester, comprise repeating unit
time, namely when preparation process Raw comprises NDA, can find, the difference of its Tc and heat-drawn wire is between 10-20 DEG C of scope, further its that resist warping performance is tested to the liquid crystal polyester of embodiment and comparative example gained, test the plectane buckling deformation amount of its injection moulding as stated above, when can find the difference of liquid crystal polyester Tc described in comparative example and heat-drawn wire higher than 20 DEG C or lower than 10 DEG C, and the plectane of its injection moulding, its buckling deformation amount is all large than embodiment, and the Tc of liquid crystal polyester in embodiment and the difference of heat-drawn wire between 10-20 DEG C of scope time, the buckling deformation amount of liquid crystal polyester can control in a good value range, the that resist warping performance of the Injection moulded part of described liquid crystal polyester is well promoted.Meanwhile, the notched Izod impact strength of the liquid crystal polyester described in embodiment is also higher than the notched Izod impact strength of liquid crystal polyester in comparative example.
This shows, the Tc of liquid crystal polyester of the present invention and the difference of heat-drawn wire can well control within certain scope, and that resist warping performance of its composition is also well improved.
As can be seen from Table 1, liquid crystal polyester heat-drawn wire of the present invention is all higher.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (9)
1. a liquid crystal polyester, comprises formula I, the repeating unit shown in (II) and (III):
——O——Ar
1——O——(Ⅱ)、
——OC——Ar
2——CO——(Ⅲ)，
Wherein, Ar
1be selected from
Ar
2comprise
The molar ratio of the repeating unit shown in formula I is 55-65%, based on whole repeating units of described liquid crystal polyester;
The molar ratio of the repeating unit shown in formula II is 17.5-22.5%, based on whole repeating units of described liquid crystal polyester;
The molar ratio of the repeating unit shown in formula III is 17.5-22.5%, based on whole repeating units of described liquid crystal polyester;
Repeating unit shown in described (III) comprises
Wherein, molar weight c, d and e of the repeating unit shown in (c), (d) He (e) meet following relationship: 0 < e/ [c+d+e]≤29%.
2. liquid crystal polyester as claimed in claim 1, is characterized in that:
Molar weight c, d and e of the repeating unit shown in described (c), (d) He (e) meet following relationship:
11.1％≤e/[c+d+e]≤28.6％。
3. liquid crystal polyester as claimed in claim 1 or 2, is characterized in that:
Repeating unit shown in described (II) comprises
Repeating unit shown in its Chinese style (b) Yu formula (a) mole ratio be 0-1.
4. liquid crystal polyester as claimed in claim 1, is characterized in that:
Described liquid crystal polyester measures heat-drawn wire for 245-305 DEG C with the heating rate of 2 DEG C/min according to ISO75-2 standard under 1.82MPa load.
5. liquid crystal polyester as claimed in claim 1, is characterized in that:
It is 10-20 DEG C that the Tc of described liquid crystal polyester deducts heat-drawn wire.
6. the preparation method of the liquid crystal polyester described in an any one of claim 1-5:
In proportion by monomer
under acetic anhydride acylating agent and catalyst action, melt polymerization prepares prepolymer, then carries out solid state polymerization and prepares liquid crystal polyester.
7. prepare the preparation method of liquid crystal polyester as claimed in claim 6, it is characterized in that:
The condition of described solid state polymerization is temperature of reaction 10-80 DEG C below prepolymer melt temperature, pressure≤200Pa; Reaction times is 1-24 hour.
8. a composition for liquid crystal polyester, comprises by the liquid crystal polyester described in any one of claim 1-5 and mineral filler.
9. a purposes for the composition of liquid crystal polyester as claimed in claim 8, it is applied to field of electronics.
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| CN201210328681.5A CN103665354B (en) | 2012-09-06 | 2012-09-06 | The application of a kind of liquid crystal polyester, its preparation method, its composition and composition thereof |
| PCT/CN2012/081587 WO2014036760A1 (en) | 2012-09-06 | 2012-09-19 | Liquid crystal polyester and preparation method thereof, composition containing the same and use of composition |
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| CN103923306B (en) * | 2014-04-08 | 2016-03-09 | 金发科技股份有限公司 | A kind of liquid crystal polyester and consisting of liquid-crystalline polyester composition and application |
| CN103910860B (en) * | 2014-04-11 | 2016-01-20 | 江苏金聚合金材料有限公司 | A kind of preparation method of degradable oxyacetic acid copolyesters |
| CN105801826A (en) * | 2014-12-29 | 2016-07-27 | 金发科技股份有限公司 | Liquid crystal polyester resin and liquid crystal polyester composition thereof |
| CN105504247A (en) * | 2015-12-30 | 2016-04-20 | 金发科技股份有限公司 | Liquid crystal polyester and liquid crystal polyester composition composed by liquid crystal polyester |
| CN105504714A (en) * | 2015-12-30 | 2016-04-20 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| CN105542135A (en) * | 2015-12-30 | 2016-05-04 | 金发科技股份有限公司 | Liquid crystal polyester and liquid crystal polyester composition consisting of same |
| CN105542136A (en) * | 2015-12-30 | 2016-05-04 | 金发科技股份有限公司 | Liquid crystal polyester and liquid crystal polyester composition consisting of same |
| CN105504697A (en) * | 2015-12-30 | 2016-04-20 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| CN105566868A (en) * | 2015-12-30 | 2016-05-11 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| CN105585828A (en) * | 2015-12-30 | 2016-05-18 | 金发科技股份有限公司 | LCP (liquid crystal polyester) composition |
| CN105837803B (en) * | 2016-02-01 | 2017-05-31 | 金发科技股份有限公司 | A kind of liquid crystal polyester and the moulding compound being made from it and its application |
| CN105838386A (en) * | 2016-04-13 | 2016-08-10 | 珠海万通特种工程塑料有限公司 | Liquid crystalline polyester composition |
| CN108102314A (en) * | 2017-12-26 | 2018-06-01 | 上海普利特化工新材料有限公司 | A kind of high temperature resistant conduction liquid crystal polyester composite |
| JP7175834B2 (en) * | 2019-04-16 | 2022-11-21 | 上野製薬株式会社 | liquid crystal polyester resin |
| CN114126847A (en) * | 2019-07-17 | 2022-03-01 | 住友化学株式会社 | Method for producing welded molded article, and pipe |
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| CN103665354A (en) | 2014-03-26 |
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Effective date of registration: 20161130 Address after: Guangdong province Zhuhai City Road nine South Town Jinwan District Petrochemical 177 Building No. 1 Patentee after: ZHUHAI WANTONG SPECIAL ENGINEERING PLASTICS CO., LTD. Address before: Ke Feng Lu Science City high tech Industrial Development Zone of Guangzhou City, Guangdong Province, No. 33 510663 Patentee before: Kingfa Technology Co., Ltd. Patentee before: Shanghai Kingfa Science and Technology Development Co., Ltd. Patentee before: Zhuhai Wantong Chemical Co., Ltd. |