CN101210068A - Method for preparing full-aromatic polyester - Google Patents
Method for preparing full-aromatic polyester Download PDFInfo
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- CN101210068A CN101210068A CNA2006101732318A CN200610173231A CN101210068A CN 101210068 A CN101210068 A CN 101210068A CN A2006101732318 A CNA2006101732318 A CN A2006101732318A CN 200610173231 A CN200610173231 A CN 200610173231A CN 101210068 A CN101210068 A CN 101210068A
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- aromatic polyester
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Abstract
The invention provides wholly aromatic polyester and a preparation method thereof which is conducted in two steps. A prepolymerization reaction is carried out to obtain prepolymer with specific grain diameter and then is followed by solid polymerization reaction. The quality of polyester is effectively controlled by the method of the invention and the wholly aromatic polyester with high fluid performance, high anti-heating property and high resistance to solder tin heat is obtained.
Description
Technical field
The invention provides a kind of full-aromatic polyester with and manufacture method, can effectively control the polyester quality according to this method, and can obtain to have high workability, the full-aromatic polyester of high heat resistance and high scolding tin heat resist.
Background technology
Melt processable liquid crystal polyester (LCP) is known by knowing this skill person.This kind liquid crystal polyester is because its excellent thermotolerance and mechanical-physical character, with and in the excellent flowable of molten state, so in various fields, be used as carrying out accurate molded moulding material.Because it manifests very high melt temperature, be applied to prepare small electronic component so mainly arrange in pairs or groups inorganic filler, as junctor, rly. etc.At the small electronic component of preparation, during as junctor, rly. etc., these material requires possess high thermal resistance, high strength, high size precision, high scolding tin heat resist simultaneously.
For the full-aromatic polyester that obtains stay in grade and make the product that contains this polyester possess high thermal resistance, high strength, high size precision, high scolding tin heat resist simultaneously, the inventor carries out broad research to the processing procedure of full-aromatic polyester, thereby finishes the present invention.
Summary of the invention
The invention provides a kind of full-aromatic polyester with and manufacture method, this method is to utilize two elementary reaction methods, carries out prepolymerization reaction earlier, institute is obtained prepolymer sieve according to screen-dividing machine and make prepolymer have specified particle diameter to distribute, carry out poly-admittedly the reaction subsequently.
The manufacture method of full-aromatic polyester of the present invention, be the m-phthalic acid of the terephthalic acid of the dihydroxybiphenyl of the benzoquinones of the hydroxy-benzoic acid that makes 35～65 moles of %, 0～10 mole of %, 15～35 moles of %, 15～35 moles of %, 0～15 mole of % and carry out the prepolymerization reaction with respect to the diacetyl oxide that total hydroxyl mole number of aforementioned composition is 1.0～1.3 times of molar weights, then the prepolymer mat sieve apparatus of gained sieves, and the size distribution of control prepolymer is in following scope:
10～39 meshes=5～20wt%;
40～59 meshes=20～40wt%;
60～79 meshes=40～70wt%;
80～120 meshes=0～15wt%;
Then the prepolymer with above-mentioned size distribution with gained carries out poly-admittedly reaction, obtains to have the full-aromatic polyester of stabilizing quality.
In the manufacture method of full-aromatic polyester of the present invention, aforementioned prepolymerization reaction is to carry out 0.5～4 hour at 140～160 ℃, the heat-up rate of following with 0.3～3 ℃/minute begins to collect the by product that distills out simultaneously from 140～160 ℃ of intensifications, up to be heated to 300 ℃ keep 0.5～3 hour after, residue is polyester prepolyer.
In the manufacture method of full-aromatic polyester of the present invention, aforementioned solid poly-reaction is the temperature rise rate with 0.05～0.3 ℃/minute, is carrying out in 250 ℃ to 320 ℃ temperature range 4-20 hour.
In the manufacture method of full-aromatic polyester of the present invention, the sieve apparatus of control prepolymer size distribution, be to utilize the shaking-sieving machine equipment, sieve that sampling obtains the size distribution in the above-mentioned scope separately with five layers of screen cloth that are respectively 10 meshes, 40 meshes, 60 meshes, 80 meshes and 120 meshes.
According to the present invention, this full-aromatic polyester is the full-aromatic polyester with repeating unit shown in the following formula:
A/ (a+b+c)=0.35～0.70 wherein; B/ (a+b+c)=0.15～0.35; C/b=0.9～1.1; M and n are respectively 0 or 1 number; X represents C
1-6Alkylidene group.
When the structural content of a indication in the full-aromatic polyester is less than 35 moles of % (a/ (a+b+c) value is less than 0.35), thermotolerance may be not enough, and when the structural content of a indication during greater than 70 moles of % (a/ (a+b+c) is worth greater than 0.70), operability can be inferior.The structure of a indication more suitably is 35 to 65 moles of %, and more suitable is 45 to 55 moles of %.When the structural content of the b of full-aromatic polyester indication during greater than 35 moles of % (b/ (a+b+c) is worth greater than 0.35), operability may be inferior, and when content during less than 15 moles (b/ (a+b+c) be worth less than 0.15), thermotolerance may deficiency.
When the ratio of the structure of the structure of c indication and b indication less than 0.9 or greater than 1.1 the time, the polymerization degree of full-aromatic polyester may be not enough, and physical properties may descend.
Among the present invention, the C shown in the X
1-6Alkylidene group means the residue that the straight chain of self-contained 1 to 6 carbon atom or branch's alkyl remove gained behind two hydrogen atoms, and the example can be given an example as methylene radical, ethylidene, straight chain or ramose propylidene, straight chain or ramose butylidene, straight chain or ramose pentylidene or straight chain or ramose hexylidene.
According to the prepared stay in grade of the inventive method with full-aromatic polyester of following formula repeating unit, and when being used for having high workability, high heat resistance and high scolding tin heat resist with the mixed composition of inorganic filler.
The present invention provides a kind of full-aromatic polyester composition again, and it comprises the full-aromatic polyester of 40～80wt% and the inorganic filler of 20～60wt%, and can be used for making small electronic component such as junctor, rly. etc.These inorganic fillers are to be selected from talcum, mica, CaSiO
3, carbon black, glass fibre, carbon fiber, synthetic polymer fiber, aluminum fiber, aluminum silicate fiber, sapphire whisker, titanium fiber, magnesium fiber, rock wool fibers, steel fiber, Calucium Silicate powder, silicon oxide and cohort that titanium dioxide is formed one or more.Though the particle diameter of inorganic filler is not particularly limited, the scope of 0.1～150 μ m more fortunately.
According to full-aromatic polyester composition of the present invention, by utilizing the prepared full-aromatic polyester of the inventive method, can obtain to possess high thermal resistance simultaneously, the product of high strength, high size precision, high scolding tin heat resist.
Embodiment
The present invention will further specify the present invention with the following example, and only these embodiment are only in order to explanation the present invention, but not in order to limit the scope of the invention.
Embodiment 1
(a) petchem prepolymerization reaction
Make right-hydroxy-benzoic acid (PHBA) 690 weight parts (50 moles of %), benzoquinones (BQ) 20 weight parts (1.8 moles of %), 4; 4 '-dihydroxybiphenyl (DOD), 430 weight parts (23.2 moles of %), terephthalic acid (TPA) 290 weight parts (17.5 moles of %), m-phthalic acid (IPA) 125 weight parts (7.5 moles of %) and diacetyl oxide 1020 weight parts (100 moles of %) are inserted in the reactor; carried out acetylization reaction 0.5 hour at 160 ℃; temperature rise rate with 0.3 ℃/min is heated to 300 ℃ subsequently, and this temperature maintenance 0.5 hour.Heat up between heating period, collect the by-product acetic acid that distills out.The residue of staying in the reactor is polyester prepolyer.The solid polyester prepolymer that is obtained utilizes pulverizer and shaking-sieving machine equipment again, sieves with four layers of screen cloth that are respectively 10 meshes, 40 meshes, 60 meshes, 80 meshes and 120 meshes, obtains the polyester prepolyer of following size distribution from each grade sampling.
10-39 mesh: 5%
40-59 mesh: 25%
60-79 mesh: 55%
80-120 mesh: 15%
(b) solid-phase polymerization of polyester prepolyer
The polyester prepolyer that will have above-mentioned size distribution is inserted in the solid-phase polymerization still, is heated to 250 ℃, again with 0.3 ℃/min of temperature rise rate be heated to 320 ℃ keep 4 hours after, obtain full-aromatic polyester.
(c) preparation of polymer blend
Use twin-screw extruder (damp machine corporate system twin-screw extruder model ZPT28) with under the rotating speed 200rpm, 340 ℃, make 70 kilograms of the polyester of step (b) gained carry out the mixing polymer blend of making for 30 kilograms, with after the yield temperature (T of pelletizing and following mensuration resin combination with glass fibre
Fb).
The polymer blend that obtained is used Jet forming machine (birch admire corporate system model HC-350CL), at 330 ℃ of tube temperature, 100 ℃ of following ejection formations of mould temperature.Test film to ejection formation carries out following folding strength, scolding tin heat resist and heat-drawn wire measurement.
1. polymer blend yield temperature (Flow Beginning Temperature:T
Fb) measurement
Resin is imposed 100kgf/cm
2Back pressure (plasticizing pressure), and flow out in the hole of resin by 1 millimeter of diameter, 10 millimeters of length with 4 ℃/min heating.Temperature when the resin melt viscosity reaches 48000Pa.s is considered as yield temperature, uses equipment to be Tianjin, island (Shimadzu) Koka of company type Flow Tester flowing test instrument model C FT-500.
2. the measurement of folding strength (Flexural Strength)
Make the polymer blend ejection formation for long 80 millimeters, wide 10 millimeters and thick 4.0 millimeters test film, according to method shown in the ASTM D790 and conditioned measurement folding strength.
3. the measurement of heat-drawn wire (Heat Deforming Temperature)
Make the polymer blend ejection formation be long 127 millimeters, wide 12.7 millimeters and thick 6.4 millimeters test film, according to the method shown in the ASTM D648 at 18.6kg/cm
2Load is measured heat-drawn wire down.
4. the scolding tin thermal impedance is measured
Make the polymer blend ejection formation be long 80 millimeters, wide 10 millimeters and thick 4 millimeters test film, test piece immersed in 288 ℃ of solder furnace 90 seconds, observe outward appearance and have or not and bubble or distortion, if having bubble or distortion then be designated as *, do not bubble or distortion then is not designated as o if having.
Embodiment 2-4
Prepare polyester prepolyer as embodiment 1 identical mode and composition, but the size distribution of prepolymer is as shown in table 1 below.Similarly, as described in embodiment 1, make polyester prepolyer carry out solid-phase polymerization and obtain polyester, and mixing with glass fibre, making polymer blend, ejection formation is made each test film and is measured above-mentioned each character subsequently.
Embodiment 5
(a) petchem prepolymerization reaction
Make right-hydroxy-benzoic acid (PHBA) 483.4 weight parts (35 moles of %), 4,4 '-dihydroxybiphenyl (DOD), 633.1 weight parts (34 moles of %), terephthalic acid (TPA) 348.9 weight parts (21 moles of %), m-phthalic acid (IPA) 166.1 weight parts (10 moles of %) and diacetyl oxide 1326 weight parts (130 moles of %) are inserted in the reactor, carry out second vinegar reaction 4 hours at 140 ℃, temperature rise rate with 3 ℃/min is heated to 300 ℃ subsequently, and this temperature maintenance 3 hours.
Heat up between heating period, collect the by-product acetic acid that distills out.The residue of staying in the reactor is polyester prepolyer.The solid polyester prepolymer that is obtained utilizes pulverizer and shaking-sieving machine equipment again, sieves with five layers of screen cloth that are respectively 10 meshes, 40 meshes, 60 meshes, 80 meshes and 120 meshes, obtains the polyester prepolyer of following size distribution from each grade sampling.
10-39 mesh: 5%
40-59 mesh: 25%
60-79 mesh: 55%
80-120 mesh: 15%
(b) solid-phase polymerization of polyester prepolyer
The polyester prepolyer that will have above-mentioned size distribution is inserted in the solid-phase polymerization still, is heated to 250 ℃, again with 0.05 ℃/min of temperature rise rate be heated to 320 ℃ keep 20 hours after, obtain polyester.
All the other follow-up making and analysis are with embodiment 1.
Embodiment 6-7
Prepare polyester prepolyer as embodiment 5 identical mode and compositions, but the size distribution of prepolymer is as shown in table 1 below.Similarly, as described in embodiment 5, make polyester prepolyer carry out solid-phase polymerization and obtain polyester, and mixing with glass fibre, making polymer blend, ejection formation is made each test film and is measured above-mentioned each character subsequently.
Comparative example 1-4
Prepare polyester prepolyer as embodiment 1 identical mode and composition, but the size distribution of prepolymer is as shown in table 1 below.Similarly, as described in embodiment 1, make polyester prepolyer carry out solid-phase polymerization and obtain polyester, and mixing with glass fibre, making polymer blend, ejection formation is made each test film and is measured above-mentioned each character subsequently.
Comparative example 3-4
Prepare polyester prepolyer as embodiment 5 identical mode and compositions, but the size distribution of prepolymer is as shown in table 1 below.Similarly, as described in embodiment 5, make polyester prepolyer carry out solid-phase polymerization and obtain polyester, and mixing with glass fibre, making polymer blend, ejection formation is made each test film and is measured above-mentioned each character subsequently.
Table 1
By the result of last table as can be known, the prepolymer size distribution of comparative example 1 is higher in the ratio of 10-40 mesh, overall big particle diameter prepolymer is more, because particle diameter is bigger, being easy to generate by product (acetate) during reaction accumulates in inside and can't discharge, make pet reaction incomplete, cause the prepared product intensity of the mixed composition of polyester and weighting agent, scolding tin heat resist thermotolerance variation.
And the prepolymer size distribution of comparative example 2 is higher in the ratio of 80～120 meshes, overall small particle size prepolymer is more, because particle diameter is less, when solid-phase polymerization heats up heating, make small-particle petchem vitreous clinker easily, causing by product to be coated can't discharge, and makes pet reaction incomplete, causes the prepared product intensity of the mixed composition of polyester and weighting agent, scolding tin heat resist thermotolerance variation equally.
And the prepolymer size distribution of embodiment 1 to 7 is in disclosed scope, carry out the polyester size distribution of poly-reaction admittedly by control, can effectively control quality, and product have high workability, high heat resistance and high scolding tin heat resist by the prepared the finished product of this polymkeric substance.
Claims (8)
1. the manufacture method of a full-aromatic polyester, be the m-phthalic acid of the hydroxy-benzoic acid that makes 35～65 moles of %, the benzoquinones of 0-10 mole %, the dihydroxybiphenyl of 15～35 moles of %, the terephthalic acid of 15～35 moles of %, 0～15 mole of % and carry out the prepolymerization reaction with respect to the diacetyl oxide that total hydroxyl mole number of aforementioned composition is 1.0～1.3 times of molar weights, then to the size distribution of the prepolymer of gained be controlled at following scope in:
10～39 meshes=5～20wt%;
40～59 meshes=20～40wt%;
60～79 meshes=40～70wt%;
80～120 meshes=0～15wt%;
Then the prepolymer with above-mentioned size distribution with gained carries out poly-admittedly reaction, obtains full-aromatic polyester.
2. method as claimed in claim 1, wherein this prepolymerization reaction is to carry out 0.5～4 hour at 140～160 ℃, the heat-up rate of following with 0.3～3 ℃/minute begins to collect the by product that distills out simultaneously from 140～160 ℃ of intensifications, up to be heated to 300 ℃ keep 0.5～3 hour after, residue is polyester prepolyer.
3. method as claimed in claim 1, wherein this solid poly-reaction is the temperature rise rate with 0.05～0.3 ℃/minute, is carrying out in 250 ℃ to 320 ℃ temperature range 4-20 hour.
4. one kind by as the prepared full-aromatic polyester of each method in the claim 1 to 3, and it has repeating unit shown in the following formula:
A/ (a+b+c)=0.35～0.70 wherein; B/ (a+b+c)=0.15～0.35; C/b=0.9～1.1; M and n are respectively 0 or 1 number; X represents C
1-6Alkylidene group.
5. full-aromatic polyester composition, it comprises the described full-aromatic polyester of claim 4 of 40～80wt% and the inorganic filler of 20～60wt%.
6. full-aromatic polyester composition as claimed in claim 5, wherein these inorganic fillers are to be selected from by talcum, mica, CaSiO
3, carbon black, glass fibre, carbon fiber, synthetic polymer fiber, aluminum fiber, aluminum silicate fiber, sapphire whisker, titanium fiber, magnesium fiber, rock wool fibers, steel fiber, Calucium Silicate powder, silicon oxide and cohort that titanium dioxide is formed one or more.
7. full-aromatic polyester composition as claimed in claim 5, wherein these inorganic filler particle diameters are in the scope of 0.1～150 μ m.
8. full-aromatic polyester composition as claimed in claim 5, it is in order to make small electronic component such as junctor, rly..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610173231A CN101210068B (en) | 2006-12-30 | 2006-12-30 | Method for preparing full-aromatic polyester |
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|---|---|---|---|
| CN200610173231A CN101210068B (en) | 2006-12-30 | 2006-12-30 | Method for preparing full-aromatic polyester |
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| CN101210068A true CN101210068A (en) | 2008-07-02 |
| CN101210068B CN101210068B (en) | 2010-05-26 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108026258A (en) * | 2015-10-21 | 2018-05-11 | 宝理塑料株式会社 | Wholly aromatic polyester and its manufacture method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3099455B2 (en) * | 1990-10-08 | 2000-10-16 | 住友化学工業株式会社 | Aromatic polyester and method for producing the same |
| TWI359159B (en) * | 2003-11-05 | 2012-03-01 | Sumitomo Chemical Co | Aromatic liquid-crystalline polyester |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108026258A (en) * | 2015-10-21 | 2018-05-11 | 宝理塑料株式会社 | Wholly aromatic polyester and its manufacture method |
| CN108026258B (en) * | 2015-10-21 | 2019-03-26 | 宝理塑料株式会社 | Wholly aromatic polyester and its manufacturing method |
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| CN101210068B (en) | 2010-05-26 |
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