CN103159943B - Method for synthesizing liquid crystal polyester by using rare earth catalyst - Google Patents
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- CN103159943B CN103159943B CN201110405689.2A CN201110405689A CN103159943B CN 103159943 B CN103159943 B CN 103159943B CN 201110405689 A CN201110405689 A CN 201110405689A CN 103159943 B CN103159943 B CN 103159943B
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Abstract
The present invention discloses a method for synthesizing a liquid crystal polyester by using a rare earth catalyst. The method comprises that: 1) at least an aromatic hydroxy carboxylic ester and at least an aromatic diol or an alicyclic diol are subjected to an acylation reaction in a reactor in the presence of an acylation agent, 2) after completing the acylation reaction, at least an aromatic dicarboxylic ester and a rare earth catalyst are added to carry out pre-polymerization to obtain a prepolymer, and 3) the obtained prepolymer from the step 2) is subjected to a solid phase tackifying reaction to obtain the liquid crystal polyester, wherein the rare earth catalyst is at least one selected from a lanthanide element, a scandium compound and a yttrium compound. According to the present invention, the rare earth metal compound is adopted as a catalyst, the aromatic dicarboxylic ester with a cost advantage is adopted, particularly dimethyl 2,6-naphthalenedicarboxylate, the aromatic hydroxy carboxylic ester, and the aromatic diol or the alicyclic diol are subjected to melting condensation polymerization, and solid phase tackifying is supplemented to obtain the liquid crystal polyester meeting molded article requirements. The synthesis process has characteristics of simpleness, easy control, and significantly reduced liquid crystal polyester production cost.
Description
Technical field
The invention belongs to material engineering field, specifically, relate to a kind of preparation method of liquid crystal polyester.
Background technology
liquid crystal polyester has excellent thermotolerance, from flame retardant properties, dimensional stability, electrical property and processing fluidity.At all fields of national economies such as space flight and aviation, electronics, automotive industrys, be all widely applied at present.Along with electron trade, developing rapidly of IT industry especially, the precise treatment of electronic unit and use the surface mounting technique of environmental-friendly lead-free scolding tin material to promote liquid crystal polyester development.
Business-like liquid crystal polyester is mainly prepared by melt polycondensation method.But because the nucleophilicity of aromatic hydroxy in its monomer aromatic diols used is very low, can not adopt the reaction of direct fusion esterification synthetic, must be first after aromatic hydroxy or aromatic carboxylic groups activation and then carry out polymerization.US5084547 report utilizes P-hydroxybenzoic acid, Resorcinol, '-biphenyl diphenol, terephthalic acid melt polymerization under diphenyl carbonate effect to prepare liquid crystal polyester.US7009026 reports and utilizes P-hydroxybenzoic acid, '-biphenyl diphenol, terephthalic acid, m-phthalic acid melt polymerization under diphenyl carbonate effect to prepare liquid crystal polyester.But the diphenyl carbonate that this method is used is expensive, and the very difficult Ex-all of the by-product phenol producing, it is more difficult that this route is realized industrialization.First current business-like liquid crystal polyester carries out acetylization reaction generation acetic ester by aromatic hydroxy and diacetyl oxide conventionally, and then obtains liquid crystal polyester by acidolysis reaction melt polymerization.The monomer that above-mentioned two kinds of routes are used needs higher purity, and price comparison is high; This certainly will increase the production cost of liquid crystal polyester.Therefore finding starting material that cost has more advantage becomes an emphasis of liquid crystal polyester exploitation.
US5731401 report is used P-hydroxybenzoic acid, Resorcinol, terephthalic acid, NDA dimethyl ester, 1-acetoxyl group-4-acetyl amino phenyl under catalysis, by melt polymerization, to prepare liquid crystal polyester altogether at Dibutyltin oxide, acetic acid or trifluoroacetic acid.The NDA dimethyl ester monomer that this method is used is simple compared with NDA purifying technique, and its price is also more cheap accordingly, thereby the cost of the liquid crystal polyester of gained also reduces accordingly; But this method need use acetic acid or trifluoroacetic acid as co-catalyst.
In recent years, rare earth compound is used the extensive concern that has caused Chinese scholars as catalyzer, especially utilize the correlation technique of lanthanide series metal catalyzer synthetic aroma, aliphatic polyester also to increase thereupon.But utilize rare earth compound also to rarely have report as the technology of the synthetic liquid crystal polyester of catalyzer.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of rare earth compound that utilizes as under catalyst action, the method for synthetic liquid crystal polyester.
To achieve these goals, the present invention adopts following technical scheme:
A method of utilizing the synthetic liquid crystal polyester of rare earth catalyst, comprises the following steps:
1) will be selected from least one aromatic hydroxy-carboxylic ester, at least one aromatic series or alicyclic dibasic alcohol; Under existing, acylating agent in reactor, carries out acylation reaction;
2), after acylation reaction completes, add at least one aromatic dicarboxylic acids's ester, rare earth catalyst to carry out prepolymerization and obtain prepolymer;
3) by 2) prepolymer that obtains carries out solid-phase tack producing reaction, obtains liquid crystal polyester;
Wherein, described rare earth catalyst is at least one in lanthanon, scandium and yttrium compound.
Liquid crystal polyester of the present invention can obtain by melt polycondensation reaction; hydroxyl reaction by acylating agent and aromatic hydroxycarboxylic acids ester, aromatic diol and/or aliphatic diol obtains acidylate material, and then acylate and aromatic dicarboxilic acid ester carry out ester hydrolysis reaction and obtain liquid crystal polyester under catalyzing of rare-earth metal exists.
In above-mentioned preparation method, the structural formula of described aromatic hydroxy-carboxylic ester is as follows:
Ar wherein
1represent one or more aromatic series base;
R is selected from C
1~ C
4alkyl.Specifically comprise: methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propylparaben, butyl p-hydroxybenzoate, 2-hydroxyl-6-2-methyl naphthoate, 2-hydroxyl-6-naphthoic acid ethyl ester, 2-hydroxyl-6-naphthoic acid propyl ester, 2-hydroxyl-6-naphthoic acid butyl ester etc.They can be used alone or in conjunction with two or more uses.Wherein obtain owing to being easy to, preferably use methyl p-hydroxybenzoate and 2-hydroxyl-6-2-methyl naphthoate.
Aromatic diol is selected from 4, and 4 '-'-biphenyl diphenol, Resorcinol, Resorcinol, alkyl replace Resorcinol; Alicyclic dibasic alcohol is 4,4 '-cyclohexanedimethanol.
The example of acylating agent comprises diacetyl oxide, propionic anhydride, butyryl oxide, isobutyric anhydride, maleic anhydride, succinyl oxide etc.Wherein preferably use 1-1.5 times that its consumption of diacetyl oxide is hydroxyl mole number in monomer, preferably 1.02-1.2 doubly.
The present invention carries out acylation reaction and preferably at 130-180 ℃, carries out 30 minutes-10 hours, more preferably at 140-150 ℃, carries out 1 hour-4 hours.
In above-mentioned preparation method, the structural formula of described aromatic dicarboxylic acids's ester is as follows:
Ar wherein
2represent one or more aromatic series base;
R
1be selected from C
1~ C
4alkyl.Specifically comprise: dimethyl terephthalate (DMT), dimethyl isophthalate, 2,6-naphthalene diformic acid dimethyl ester, 4,4 '-biphenyl dicarboxylic acid dimethyl ester, diethyl terephthalate, dimethyl isophthalate, 2,6-naphthalic acid diethyl ester, 4,4 '-biphenyl dicarboxylic acid diethyl ester, terephthalic acid dipropyl, m-phthalic acid dipropyl, 2,6-naphthalic acid dipropyl, 4,4 '-biphenyl dicarboxylic acid dipropyl, dibutyl terephthalate, m-phthalic acid dibutylester, 2,6-naphthalic acid dibutylester, 4,4 '-biphenyl dicarboxylic acid dibutylester etc.Wherein preferably use dimethyl terephthalate (DMT), dimethyl isophthalate, NDA dimethyl ester, 4,4 '-biphenyl dicarboxylic acid dimethyl ester.
The mol ratio of aromatic diol of the present invention or alicyclic dibasic alcohol and aromatic dicarboxilic acid ester is 1:1.1 ~ 1.1:1, and the mol ratio of dibasic alcohol and dicarboxylic esters sum and aromatic hydroxycarboxylic acid ester is 30:70 ~ 50:50.
The method steps 2 of synthetic liquid crystal polyester of the present invention) in, rare-earth compound used is selected from the halogenide LnX of rare earth metal
3, the hydrochlorate Ln(R of institute
1cOO)
3, alkyl oxide Ln(OR
2)
3, sulfonic group compound L n(SOR
3)
3, acetylacetonate compound Ln(a
ca
c)
3and at least one in their hydrate, wherein X is halide-ions, preferably chlorine, bromide anion.R
1be selected from C
1~ C
18alkyl, preferable methyl; R
2be selected from C
3~ C
8alkyl; Preferred normal-butyl, n-octyl; R
3be selected from C
1~ C
8alkyl and substituted alkyl, preferable methyl, trifluoromethyl; a
ca
cfor methyl ethyl diketone group.
The rare earth element of wherein said rare earth catalyst is selected from lanthanum La, neodymium Nd, cerium Ce, dysprosium Dy, scandium Sc and yttrium Y, preferably lanthanum La, neodymium Nd.
Rare earth catalyst dosage is 0.001 ~ 2% of total monomer weight, preferably 0.01 ~ 0.5%, more preferably 0.025 ~ 0.2%.
Step 2) ester hydrolysis reaction is preferably in the speed rising temperature of 0.1 ~ 10 ℃/min, carries out under within the scope of 130 ~ 400 ℃, more preferably in 0.5 ~ 2 ℃/min speed rising temperature, carries out under within the scope of 150 ~ 350 ℃.
Step 2) logarithmic viscosity number of gained prepolymer can be measured in Pentafluorophenol.Logarithmic viscosity number at 60 ℃ in Pentafluorophenol is at 0.5-3dL/g, preferably 1-2dL/g.
The reaction conditions of step 3) be prepolymer at 250-310 ℃, preferred 270-300 ℃; Pressure 25-1000Pa, preferably 25-100Pa; React and within 3-5 hour, obtain liquid crystal polyester; The logarithmic viscosity number of gained liquid crystal polyester is 2-10dL/g, preferably 3-6dL/g.
The melt temperature that liquid crystal polyester of the present invention is measured according to differential scanning calorimeter (DSC) is 300-380 ℃, can be used for making moulded parts and for electronic apparatus and other precision equipment field.
The present invention has following advantage and effect with respect to prior art:
It is catalyzer that the synthetic method of liquid crystal polyester of the present invention adopts rare earth compound, utilization has more the aromatic dicarboxilic acid ester of cost advantage, especially NDA dimethyl ester and aromatic hydroxycarboxylic acid ester and aromatic diol or alicyclic diol by melt phase polycondensation and be aided with that solid-phase tack producing obtains can be for the liquid crystal polyester of moulded parts requirement.This synthesis technique is simple, is easy to control, and can obviously reduces the production cost of liquid crystal polyester.
Embodiment
Illustrate in greater detail by the following examples the present invention, but the invention is not restricted to this.The method of the physical property measurement in embodiment is as described below.
Melt temperature test: melt temperature is measured by the resistance to DSC of speeding 200 F3 of Germany, is warming up to 400 ℃ with 20 ℃/min, is then cooled to 40 ℃ with 20 ℃/min speed, then is warming up to 400 ℃ with 20 ℃/min speed.Melting point polymer temperature is obtained by the attached software processes of this instrument.
Take Pentafluorophenol as solvent (concentration is the solution of 0.1 wt%), and measuring temperature is 60 ℃, and the diameter of dark type viscometer is 0.7mm, and I.V. is by formula I.V.=[ln (η
r)]/C calculates gained, wherein η
rfor relative viscosity (t
solution/ t
solvent), C represents strength of solution.
The crystallization shape of polymkeric substance and liquid crystal state texture are observed by under PLM with heating stage.
Embodiment 1
(1) prepolymer is synthetic
Is being furnished with N
2in the reactor of gas entrance, condenser and the agitator that shows with power of agitator, after nitrogen replacement three times, add 760.8g(5mol) methyl p-hydroxybenzoate (MHB); 565.5 g(2.5mol) '-biphenyl diphenol (BP); 1072g(10.5mol) diacetyl oxide (AA); And then under nitrogen gas stream, the temperature of reaction system is elevated to 145 ℃ of back flow reaction 3 hours; In 0.5 hour, temperature being risen to 200 ℃ also steams except by-product acetic acid.Next add 366.4g(1.5mol) NDA dimethyl ester (MNDC), 194.2g(1mol) dimethyl terephthalate (DMT) (DMT) and 0.943g acetic acid neodymium; In 150 minutes, be warming up to 305 ℃ subsequently, remove by product acetic acid, methyl alcohol and unreacted acetic anhydride, at 305 ℃, insulation reaction is 30 minutes.Then be warmed up to 335 ℃ of reactions, after 0.5 hour, condenser changed into vacuum extractor, slowly gas clean-up is polymerized to the moment of torsion of predeterminated level.Then replace nitrogen.Taking out prepolymer pulverizes and obtains particulate state prepolymer with Universalpulverizer.The melt temperature of the prepolymer of measuring by dsc is 327 ℃, and the logarithmic viscosity number of measuring in Pentafluorophenol is 2.2dL/g.
(2) solid state polymerization
Prepolymer is 120 ℃ of vacuum-dryings 2 hours, then join can the device of pumping high vacuum in, be heated to 285 ℃, under 40Pa condition, react and within 4 hours, obtain polymkeric substance.This polymkeric substance is demonstrating anisotropy while observing in molten state under the polarizing microscope of hot platform by being equipped with.The melt temperature of this liquid crystal polyester is 330 ℃; The logarithmic viscosity number of measuring in Pentafluorophenol is 4.5dL/g.
Embodiment 2
(1) prepolymer is synthetic
With 0.943g methyl ethyl diketone lanthanum, as catalyzer, with the method that embodiment 1 is identical, enter polymerization, the melt temperature of the prepolymer of measuring by dsc is 327 ℃, and the logarithmic viscosity number of measuring in Pentafluorophenol is 2.2dL/g.
(2) solid state polymerization
With the identical method for solid phase polymerization of embodiment 1, resulting polymers also demonstrates anisotropy while observing in molten state under the polarizing microscope of hot platform being equipped with.The melt temperature of this liquid crystal polyester is 331 ℃; The logarithmic viscosity number of measuring in Pentafluorophenol is 4.1dL/g.
Embodiment 3
(1) prepolymer is synthetic
With 0.943g Lanthanum trichloride, as catalyzer, with the method that embodiment 1 is identical, enter polymerization, the melt temperature of the prepolymer of measuring by dsc is 323 ℃, and the logarithmic viscosity number of measuring in Pentafluorophenol is 1.3dL/g.
(2) solid state polymerization
With the identical method for solid phase polymerization of embodiment 1, resulting polymers also demonstrates anisotropy while observing in molten state under the polarizing microscope of hot platform being equipped with.The melt temperature of this liquid crystal polyester is 328 ℃; The logarithmic viscosity number of measuring in Pentafluorophenol is 2.6dL/g.
Comparative example 1
With 0.943g magnesium acetate, as catalyzer, with the method that embodiment 1 is identical, enter polymerization, reaction system presents brown nonhomogeneous system in the later stage.
Embodiment 4
(1) prepolymer is synthetic
Is being furnished with N
2in the reactor of gas entrance, condenser and the agitator that shows with power of agitator, after nitrogen replacement three times, add 760.8g(5mol) MHB; 202.2g(1mol) 2-hydroxyl-6-2-methyl naphthoate (MHN); 220.2g(2mol) Resorcinol (HQ); 1072g(10.5mol) diacetyl oxide (AA); And then under nitrogen gas stream, the temperature of reaction system is elevated to 145 ℃ of back flow reaction 3 hours; In 0.5 hour, temperature being risen to 200 ℃ also steams except by-product acetic acid.Next add 244.3g(1mol) MNDC, 194.2g(1mol) DMT and 0.81g methyl ethyl diketone lanthanum; In 150 minutes, be warming up to 305 ℃ subsequently, remove by product acetic acid, methyl alcohol and unreacted acetic anhydride, at 305 ℃, insulation reaction is 30 minutes.Then be warmed up to 335 ℃ of reactions, after 0.5 hour, condenser changed into vacuum extractor, slowly gas clean-up is polymerized to the moment of torsion of predeterminated level.Then replace nitrogen.Taking out prepolymer pulverizes and obtains particulate state prepolymer with Universalpulverizer.The melt temperature of the prepolymer of measuring by dsc is 315 ℃, and the logarithmic viscosity number of measuring in Pentafluorophenol is 2.0dL/g.
(2) solid state polymerization
Prepolymer is 120 ℃ of vacuum-dryings 2 hours, then join can the device of pumping high vacuum in, be heated to 270 ℃, under 40Pa condition, react and within 4 hours, obtain polymkeric substance.This polymkeric substance is demonstrating anisotropy while observing in molten state under the polarizing microscope of hot platform by being equipped with.The melt temperature of this liquid crystal polyester is 322 ℃; The logarithmic viscosity number of measuring in Pentafluorophenol is 4.2dL/g.
Embodiment 5
(1) prepolymer is synthetic
Is being furnished with N
2in the reactor of gas entrance, condenser and the agitator that shows with power of agitator, after nitrogen replacement three times, add 912.9g(6mol) MHB; 220.2g(2mol) HQ; 1072g(10.5mol) diacetyl oxide (AA); And then under nitrogen gas stream, the temperature of reaction system is elevated to 145 ℃ of back flow reaction 3 hours; In 0.5 hour, temperature being risen to 200 ℃ also steams except by-product acetic acid.Next add 244.3g(1mol) MNDC, 97.1g(0.5mol) DMT,, 97.1g(0.5mol) dimethyl isophthalate (IMT) and 0.79g methyl ethyl diketone lanthanum; In 150 minutes, be warming up to 305 ℃ subsequently, remove by product acetic acid, methyl alcohol and unreacted acetic anhydride, at 305 ℃, insulation reaction is 30 minutes.Then be warmed up to 335 ℃ of reactions, after 0.5 hour, condenser changed into vacuum extractor, slowly gas clean-up is polymerized to the moment of torsion of predeterminated level.Then replace nitrogen.Taking out prepolymer pulverizes and obtains particulate state prepolymer with Universalpulverizer.The melt temperature of the prepolymer of measuring by dsc is 335 ℃, and the logarithmic viscosity number of measuring in Pentafluorophenol is 2.3dL/g.
(2) solid state polymerization
Prepolymer is 120 ℃ of vacuum-dryings 2 hours, then join can the device of pumping high vacuum in, be heated to 280 ℃, under 40Pa condition, react and within 4 hours, obtain polymkeric substance.This polymkeric substance is demonstrating anisotropy while observing in molten state under the polarizing microscope of hot platform by being equipped with.The melt temperature of this liquid crystal polyester is 339 ℃; The logarithmic viscosity number of measuring in Pentafluorophenol is 4.3dL/g.
Claims (6)
1. a method of utilizing the synthetic liquid crystal polyester of rare earth catalyst, is characterized in that comprising the following steps:
1) will be selected from least one aromatic hydroxy-carboxylic ester, at least one aromatic series or alicyclic dibasic alcohol; Under existing, acylating agent in reactor, carries out acylation reaction;
2), after acylation reaction completes, add at least one aromatic dicarboxylic acids's ester, rare earth catalyst to carry out prepolymerization and obtain prepolymer;
3) by 2) prepolymer that obtains carries out solid-phase tack producing reaction, obtains liquid crystal polyester
Wherein, described rare earth catalyst is at least one in lanthanon, scandium and yttrium compound;
Described in step 1), aromatic hydroxy-carboxylic ester is methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propylparaben, butyl p-hydroxybenzoate, 2-hydroxyl-6-2-methyl naphthoate, 2-hydroxyl-6-naphthoic acid ethyl ester, 2-hydroxyl-6-naphthoic acid propyl ester, 2-hydroxyl-6-naphthoic acid butyl ester;
Step 2) described aromatic diol is 4, and 4 '-'-biphenyl diphenol, Resorcinol, Resorcinol and alkyl replace Resorcinol; Described alicyclic dibasic alcohol is 4,4 '-cyclohexanedimethanol;
Described in step 3), aromatic dicarboxylic acids's ester is dimethyl terephthalate (DMT), dimethyl isophthalate, 2,6-naphthalene diformic acid dimethyl ester, 4,4 '-biphenyl dicarboxylic acid dimethyl ester, diethyl terephthalate, dimethyl isophthalate, 2,6-naphthalic acid diethyl ester, 4,4 '-biphenyl dicarboxylic acid diethyl ester, terephthalic acid dipropyl, m-phthalic acid dipropyl, 2,6-naphthalic acid dipropyl, 4,4 '-biphenyl dicarboxylic acid dipropyl, dibutyl terephthalate, m-phthalic acid dibutylester, 2,6-naphthalic acid dibutylester, 4,4 '-biphenyl dicarboxylic acid dibutylester;
Wherein, according to the acylation reaction described in step 1), at 130-180 ℃, carry out 30 minutes-10 hours;
According to step 2) described ester hydrolysis reaction is in the speed rising temperature of 0.1 ~ 10 ℃/min, carries out under within the scope of 130 ~ 400 ℃;
According to the reaction conditions described in step 3) be prepolymer at 250-310 ℃, pressure 25-1000Pa, reacts and within 3-5 hour, obtains liquid crystal polyester;
Wherein rare earth catalyst dosage is per total wt 0.001 ~ 2%.
2. method according to claim 1, is characterized in that, in described step 1), acylating agent used is diacetyl oxide, and the consumption of diacetyl oxide is 1.02-1.2 times of hydroxyl mole number in monomer.
3. method according to claim 1, is characterized in that, the rare earth element of described rare earth catalyst is selected from lanthanum La, neodymium Nd, cerium Ce, dysprosium Dy, scandium Sc and yttrium Y.
4. method according to claim 1, is characterized in that, described rare-earth compound is selected from the halogenide LnX of rare earth metal
3, carboxylate salt Ln(R
1cOO)
3, alkyl oxide Ln(OR
2)
3, sulfonic group compound L n(SOR
3)
3, acetylacetonate compound Ln(a
ca
c)
3and at least one in their hydrate,
Wherein X is halide-ions, a
ca
cfor methyl ethyl diketone group,
R
1be selected from C
1~ C
18alkyl, R
2be selected from C
3~ C
8alkyl; R
3be selected from C
1~ C
8alkyl and substituted alkyl.
5. method according to claim 1, the mol ratio that it is characterized in that described aromatic diol or alicyclic dibasic alcohol and aromatic dicarboxilic acid ester is 1:1.1 ~ 1.1:1, and the mol ratio of dibasic alcohol and dicarboxylic esters sum and aromatic hydroxy-carboxylic ester is 30:70 ~ 50:50.
6. method according to claim 1, is characterized in that, described step 2) temperature of reaction system reach 200 ℃ and distillate after acylation reaction by product, add rare earth catalyst or aromatic dicarboxylic acids's ester, rare earth catalyst.
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