CN110724367B - Liquid crystal polymer/PET in-situ composite polyester material capable of being extruded into film and preparation method thereof - Google Patents
Liquid crystal polymer/PET in-situ composite polyester material capable of being extruded into film and preparation method thereof Download PDFInfo
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The invention discloses a liquid crystal polymer/PET in-situ composite polyester material capable of being extruded to form a film and a preparation method thereof. The in-situ composite polyester is obtained by blending liquid crystal polymer, PET and PET-liquid crystal polymer copolymer, and the in-situ composite polyester contains (1)60-99 parts by weight of liquid crystal polymer; (2)1-40 parts by weight of PET; (3)1-10 parts by weight of a PET-liquid crystalline polymer copolymer. The obtained composite polyester can be used for preparing a composite polyester film through extrusion film forming. The composite polyester has excellent film forming property, and the prepared film has excellent mechanical strength, heat resistance and barrier property.
Description
Technical Field
The invention relates to a liquid crystal polymer/PET in-situ composite polyester material capable of being extruded to form a film, and belongs to the technical field of composite materials.
Background
Thermotropic Liquid Crystalline Polymers (LCP) are high performance polymeric materials generally known for their high strength, high modulus, excellent melt-processing characteristics, inherent flame retardancy, low water absorption, chemical resistance and good radiation resistance and for many uses at high temperatures.
LCP can be prepared into a film product as known in the prior art, and the LCP film has the characteristics of high strength, high gas barrier, high and low temperature resistance and the like and can be applied to the field of packaging materials; in addition, with the overall advance of the application of the 5G technology, the communication frequency is further improved, and the LCP film material has low dielectric constant and low and stable dielectric loss under high frequency, so that the LCP film material can not be replaced in communication base stations and mobile terminals.
LCP molecular structure is a rigid chain segment, which is in a liquid crystal state in a melting state, has excellent fluidity, high strength and high rigidity of a finished product, but also has anisotropic defects; and the molding processing temperature is high, the viscosity is rapidly reduced after the melting is started, the shape is difficult to maintain after the extrusion molding, and the process requirement on processing equipment is high. In addition, the price is high.
At present, the LCP extrusion blow molding film forming or stretching film forming process has certain problems all over the world, and has low yield and low qualification rate. From the market demand, LCP polyester film products which maintain excellent heat resistance, mechanical properties and dielectric properties of LCP, and are low in price and easy to process are needed.
The design idea of the invention is to develop the in-situ composite material mainly aiming at the defects of LCP from the viewpoint of meeting the performances. The composite material is prepared by adopting PET with the melting temperature similar to that of LCP, preparing LCP-PET copolymer by ester exchange reaction, then melting and blending the LCP-PET copolymer with the LCP and the PET, and extruding and granulating the mixture by a double-screw extrusion device. The composite material can be used for preparing LCP composite polyester films with low processing temperature and small anisotropy.
Disclosure of Invention
The invention aims to provide a liquid crystal polymer composite polyester material. Furthermore, it is an object to conveniently extrude into a film using such materials.
The purpose of the invention can be realized by the following technical scheme:
an extrudable film-forming liquid crystal polymer/PET in-situ composite polyester material comprises the following raw materials in parts by weight:
(1)60-99 parts by weight of a liquid crystalline polymer;
(2)1-40 parts by weight of PET;
(3)1-10 parts by weight of a PET-liquid crystalline polymer copolymer.
The liquid crystal polymer in the invention is liquid crystal polyester which shows liquid crystallinity in a molten state, and the melting peak temperature of the liquid crystal polyester used in the invention is 260-350 ℃, preferably 280-330 ℃.
More specifically, the melt viscosity of the liquid crystalline polyester is usually 10 to 80 pas, preferably 25 to 60 pas. The liquid crystal polyester is a liquid crystal polyester obtained by using an aromatic compound as a raw material monomer, and preferably is a wholly aromatic liquid crystal polyester obtained by using only an aromatic compound as a raw material monomer.
As a typical example of the liquid crystal polymer of the present invention, a liquid crystal polyester obtained by polymerizing an aromatic hydroxycarboxylic acid and at least one compound selected from the group consisting of aromatic dicarboxylic acids and aromatic diols can be used. More specifically, a part or all of the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, and the aromatic diol may be each independently a polymerizable derivative thereof.
Examples of the polymerizable derivative of a compound having a hydroxyl group such as an aromatic hydroxycarboxylic acid and an aromatic diol include an acylated compound in which a hydroxyl group is acylated and converted to an acyloxy group.
The liquid crystal polyester preferably has a repeating unit represented by formula (1), formula (2) and formula (3) (hereinafter referred to as "repeating unit (1)", "repeating unit (2)" and "repeating unit (3)"):
formula (1) -O-Ar1-CO-
Formula (2) -CO-Ar2-CO-
Formula (3) -O-Ar3-O-
Wherein Ar1, Ar2 and Ar3 each independently represent a phenylene group or a naphthylene group.
In the combination of the respective repeating units constituting the liquid-crystalline polyester as described above:
the repeating unit (1) is selected from the repeating units of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; the repeating unit (2) is selected from the repeating units of terephthalic acid, isophthalic acid and 2, 6-naphthalene dicarboxylic acid, preferably from the repeating units of terephthalic acid and 2, 6-naphthalene dicarboxylic acid; the repeating unit (3) is selected from the group consisting of a repeating unit of hydroquinone, 2, 6-naphthalenediol, 4' -dihydroxybiphenyl, preferably a repeating unit derived from hydroquinone, 2, 6-naphthalenediol.
The content of the repeating unit (1) is usually 30 mol% or more, preferably 42 to 88 mol%, more preferably 58 to 72 mol%. The content of the repeating unit (2) is usually 30 mol% or less, preferably 6 to 30 mol%, more preferably 9 to 21 mol%. The content of the repeating unit (3) is usually 30 mol% or less, preferably 6 to 30 mol%, more preferably 9 to 21 mol%.
The ratio of the content of the repeating unit (2) to the content of the repeating unit (3) is usually 0.9/1 to 1/0.9, and is preferably the same.
The repeating units (1) to (3) in the liquid-crystalline polyester are each independently 1 repeating unit or a combination of 2 or more repeating units.
The repeating units (1) to (3) in the liquid crystal polyester contain at least one 1 or more kinds of repeating units containing a naphthylene group. Wherein the sum of the contents of the repeating units containing a naphthylene group is 30 to 40%.
The melting peak temperature of the PET in the invention is between 260 and 280 ℃; the melt viscosity is between 30 and 100 Pa.s.
The preparation method of the liquid crystal polymer/PET in-situ composite polyester material capable of being extruded into a film comprises the following steps:
(1) preparation of PET-liquid Crystal Polymer copolymer: putting PET, liquid crystal polymer and catalyst into a reaction kettle according to the weight ratio of 40-60:40-60:0.01-1 for blending; heating the blend above its melting point while evacuating; obtaining the PET-liquid crystal polymer copolymer after 2-8 hours.
The catalyst used may be a general basic catalyst such as potassium hydroxide, sodium methoxide, organic amine, or the like; and acidic catalysts such as concentrated sulfuric acid and sulfonic acid or mixtures thereof, phosphates, zirconium sulfate, tin sulfate, zirconium oxide, zirconium tungstate, and the like.
(2) Adding PET, a liquid crystal polymer and a PET-liquid crystal polymer copolymer into a high-speed mixer, and mixing for 3-5 minutes at normal temperature to obtain a mixture;
(3) adding the mixture into a double-screw extruder, fully melting and mixing to obtain a blend melt, and extruding and granulating to obtain in-situ composite polyester; the working temperature of the extruder was: 230 +/-5 ℃ in the first zone, 240 +/-5 ℃ in the second zone, 260 +/-5 ℃ in the third zone, 275 +/-5 ℃ in the fourth zone, 285 +/-5 ℃ in the fifth zone, 290 +/-5 ℃ in the sixth zone and 285 +/-5 ℃ in the seventh zone.
The liquid crystal polymer composite polyester material can be prepared into a liquid crystal polymer composite polyester film by a known extrusion blow molding or extrusion biaxial stretching molding method.
The liquid crystal polymer in-situ composite polyester material obtained by the invention has low required processing temperature and easy control in the process of extrusion film forming, and the obtained film material has small anisotropy, good strength and high temperature resistance. The processing of the liquid crystal polymer in-situ composite polyester material overcomes the difficulty that the liquid crystal polymer material is high in temperature and difficult to process when the liquid crystal polymer material is formed into a film; the defects that the anisotropy of the formed film is large and the practical use is influenced are overcome.
Detailed Description
The present invention is further illustrated by the following examples and comparative examples, but the present invention should not be limited to the contents specifically illustrated in the following examples without departing from the spirit of the present invention.
The product performance testing method comprises the following steps:
the melting point (T) is measured using a differential scanning calorimeter (DSC 8000, PerkinElmer, USA)m) Testing was performed according to ASTM D3418. The Melt Viscosity (MV) was measured using a capillary rheometer (RH 2200, Malvern, UK) according to ASTM D3835.
Example 1:
synthesis of prepolymer 1:
firstly, reacting p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, hydroquinone and acetic anhydride at the constant temperature of 120-130 ℃ for 1 hour, then increasing the temperature to 185-195 ℃ within 2 hours, then reacting at the constant temperature for 0.5-1 hour, and finishing the acetylation reaction; then carrying out melt polycondensation reaction on the acetic ester obtained by acetylation reaction and the naphthalenedicarboxylic acid, and heating the polymerization temperature to a preset temperature within 3 hours to continuously carry out the polymerization reaction; then keeping the temperature to enable the reactants to become a prepolymer with a certain molecular weight; when the torque of the stirrer rises to a preset degree, immediately introducing nitrogen, and stopping the polymerization reaction; increasing the nitrogen pressure to 2kg/cm2Discharging the liquid crystal polymer prepolymer, and measuring the melting point and the melt viscosity of the obtained liquid crystal polymer prepolymer. The monomer ratio for preparing the liquid crystal polymer is as follows: 32 mol% of p-hydroxybenzoic acid, 32 mol% of 6-hydroxy-2-naphthoic acid, and 18 mol% of hydroquinoneAnd 18 mol% of naphthalenedicarboxylic acid. The liquid crystalline polymer prepolymer 1 prepared had a melting point of 281 ℃ and a melt viscosity of 12 pas and was called LCP 1.
Heating the obtained prepolymer 1 from 25 ℃ to 105 ℃ for 1 hour, and then preserving the heat for 10 min; then the temperature is raised from 105 ℃ to 240 ℃ for 1 hour, and the temperature is kept for 10 min. Then, the temperature was raised from 240 ℃ to 250 ℃ over 2 hours, and the temperature was maintained for 1 hour to conduct solid-phase polymerization, followed by further cooling, whereby LCP2 was obtained.
LCP2 has a melting point of 283 ℃ and a melt viscosity of 50 pas.
Example 2:
firstly, reacting p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, hydroquinone and acetic anhydride at the constant temperature of 120-130 ℃ for 1 hour, then increasing the temperature to 185-195 ℃ within 2 hours, then reacting at the constant temperature for 0.5-1 hour, and finishing the acetylation reaction; then carrying out melt polycondensation reaction on the acetic ester obtained by acetylation reaction and the naphthalenedicarboxylic acid, and heating the polymerization temperature to a preset temperature within 3 hours to continuously carry out the polymerization reaction; then keeping the temperature to enable the reactants to become a prepolymer with a certain molecular weight; when the torque of the stirrer rises to a preset degree, immediately introducing nitrogen, and stopping the polymerization reaction; increasing the nitrogen pressure to 2kg/cm2Discharging the liquid crystal polymer prepolymer, and measuring the melting point and the melt viscosity of the obtained liquid crystal polymer prepolymer. The monomer ratio for preparing the liquid crystal polymer is as follows: 32 mol% of p-hydroxybenzoic acid, 26 mol% of 6-hydroxy-2-naphthoic acid, 21 mol% of hydroquinone, and 21 mol% of naphthalenedicarboxylic acid. The resulting liquid crystalline polymer was prepared with a melting point of 262 ℃ and a melt viscosity of 45 pas and was designated LCP 3.
Example 3:
synthesis of prepolymer 2:
prepolymer 2 was prepared in the same manner as prepolymer 1. The monomer ratio for preparing the liquid crystal polymer prepolymer 2 is as follows: 36 mol% of p-hydroxybenzoic acid, 34 mol% of 6-hydroxy-2-naphthoic acid, 15 mol% of hydroquinone and 15 mol% of terephthalic acid. The melting point of the prepared liquid crystal polymer prepolymer 2 is 325 ℃, and the melt viscosity is 6 pas.
Heating the obtained prepolymer 2 from 25 ℃ to 105 ℃ for 1 hour, and then preserving the heat for 10 min; then the temperature is raised from 105 ℃ to 240 ℃ for 1 hour, and the temperature is kept for 10 min. Then, the temperature was raised from 240 ℃ to 260 ℃ over 3 hours, and the temperature was maintained for 20 hours to conduct solid-phase polymerization, followed by further cooling, whereby LCP4 was obtained.
The melting point of LCP4 was 328 ℃ and the melt viscosity was 29 pas.
Example 4:
synthesis of prepolymer 3:
prepolymer 3 was prepared in the same manner as prepolymer 1. The monomer ratio for preparing the liquid crystal polymer prepolymer 3 is as follows: 64 mol% of p-hydroxybenzoic acid, 18 mol% of 6-hydroxy-2-naphthoic acid, 9 mol% of hydroquinone, and 9 mol% of terephthalic acid. The melting point of the prepared liquid crystal polymer prepolymer 2 is 357 ℃, and the melt viscosity is 16 pas.
Heating the obtained prepolymer 3 from 25 ℃ to 105 ℃ for 1 hour, and then preserving the heat for 10 min; then the temperature is raised from 105 ℃ to 240 ℃ for 1 hour, and the temperature is kept for 10 min. Then, the temperature was raised from 240 ℃ to 260 ℃ over 3 hours, and the temperature was maintained for 8 hours to conduct solid-phase polymerization, followed by further cooling, whereby LCP5 was obtained.
The melting point of LCP5 was 358 ℃ and the melt viscosity was 31 pas.
Example 5
Synthesis of LCP-PET copolymer:
the preparation method comprises the following steps: (1) putting PET, the liquid crystal polymer prepared by the method and a catalyst A in a weight ratio of 50:50:0.06 into a reaction kettle for blending; (2) heating the blend above its melting point while evacuating; (3) obtaining the PET-liquid crystal polymer copolymer after 2-8 hours.
The melting peak temperature of the used PET is between 260 ℃ and 280 ℃, wherein the melt viscosity of the PET1 is 63 Pa.s, and the melt viscosity of the PET2 is 25 Pa.s.
The resulting PET-liquid crystalline polymer copolymer composition is shown in Table 1:
TABLE 1 LCP-PET Components
The preparation method of the liquid crystal polymer in-situ composite polyester material comprises the following steps:
examples 6 to 9 and comparative examples 1 to 3
(1) Adding PET, a liquid crystal polymer and a PET-liquid crystal polymer copolymer into a high-speed mixer, and mixing for 3-5 minutes at normal temperature to obtain a mixture; (2) adding the mixture into a double-screw extruder, fully melting and mixing to obtain a blend melt, and extruding and granulating to obtain in-situ composite polyester; the working temperature of the extruder was: 230 +/-5 ℃ in the first zone, 240 +/-5 ℃ in the second zone, 260 +/-5 ℃ in the third zone, 275 +/-5 ℃ in the fourth zone, 285 +/-5 ℃ in the fifth zone, 290 +/-5 ℃ in the sixth zone and 285 +/-5 ℃ in the seventh zone.
Example 10
(1) Adding PET, a liquid crystal polymer and a PET-liquid crystal polymer copolymer into a high-speed mixer, and mixing for 3-5 minutes at normal temperature to obtain a mixture; (2) adding the mixture into a double-screw extruder, fully melting and mixing to obtain a blend melt, and extruding and granulating to obtain in-situ composite polyester; the working temperature of the extruder was: first zone 260 + -5 deg.C, second zone 300 + -5 deg.C, third zone 310 + -5 deg.C, fourth zone 320 + -5 deg.C, fifth zone 330 + -5 deg.C, sixth zone 335 + -5 deg.C, and seventh zone 330 + -5 deg.C.
Comparative example 4
(1) Adding PET, a liquid crystal polymer and a PET-liquid crystal polymer copolymer into a high-speed mixer, and mixing for 3-5 minutes at normal temperature to obtain a mixture; (2) adding the mixture into a double-screw extruder, fully melting and mixing to obtain a blend melt, and extruding and granulating to obtain in-situ composite polyester; the working temperature of the extruder was: the first zone is 300 +/-5 ℃, the second zone is 330 +/-5 ℃, the third zone is 340 +/-5 ℃, the fourth zone is 350 +/-5 ℃, the fifth zone is 360 +/-5 ℃, the sixth zone is 365 +/-5 ℃ and the seventh zone is 360 +/-5 ℃.
The liquid crystal polymer in-situ composite polyester material prepared by the method is prepared into a liquid crystal polymer composite polyester film by a known extrusion blow molding or extrusion biaxial stretching molding method.
The raw material ratios, film forming properties and film properties of examples 6 to 11 and comparative examples 1 to 4 are shown in Table 2. If the viscosity of the LCP or PET is too low, the composite material cannot be stably extruded into a film. If the PET-liquid crystal polymer copolymer is not added, the composite material cannot be stably extruded into a film. If the melting point of LCP is too high, a film can be formed, but the processing is difficult, and the prepared film product has large anisotropy and cannot be practical.
TABLE 2 in-situ composite polyester Material Components and Properties
In the table, a circle represents a stable extrusion film formation; x represents the inability to stably extrude into a film.
As can be seen from the table, for the examples and comparative examples, using the liquid crystal polymer, PET, whose melt viscosity and melting temperature are within a certain range, extrusion film formation can be stably performed, and the prepared film has high strength and small anisotropy.
The liquid crystal polymer in-situ composite material can be conveniently and stably extruded to form a film, and the prepared film has the characteristics of high strength and small anisotropy, so that the liquid crystal polymer in-situ composite material can be suitable for the field of food packaging or high-frequency communication.
Claims (5)
1. An extrudable film-forming liquid crystal polymer/PET in-situ composite polyester material, characterized in that: the composition comprises the following raw materials in parts by weight:
(1)60 to 88 parts by weight of a liquid crystalline polymer;
(2) 15-30 parts by weight of PET;
(3) 2-10 parts by weight of a PET/liquid crystal polymer copolymer;
the liquid crystal polymer is liquid crystal polyester which shows liquid crystallinity in a molten state, the melting peak temperature of the liquid crystal polyester is 283-350 ℃, and the melt viscosity of the liquid crystal polyester is 29-80 Pa.s;
the liquid crystalline polyester has a repeating unit (1), a repeating unit (2), and a repeating unit (3), wherein:
the repeating unit (1) is a repeating unit of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and the content is 42-88 mol%; the repeating unit (2) is a repeating unit of 2, 6-naphthalene dicarboxylic acid, and the content is 6-30 mol%; the repeating unit (3) is a repeating unit of hydroquinone, and the content is 6-30 mol%;
the ratio of the content of the repeating unit (2) to the content of the repeating unit (3) is 0.9/1 to 1/0.9;
the repeating units (1) to (3) in the liquid crystal polyester at least contain 1 or more than 1 repeating unit containing naphthylene; wherein the sum of the contents of the repeating units containing naphthylene is 30-40%;
the melting peak temperature of the PET is between 260 and 280 ℃; the melt viscosity is between 30 and 100 Pa.s.
2. The process for preparing an extrudable film-forming liquid crystalline polymer/PET in situ composite polyester material as claimed in claim 1, comprising the steps of:
(1) preparation of PET/liquid crystalline Polymer copolymer: putting PET, liquid crystal polymer and catalyst into a reaction kettle according to the weight ratio of 40-60:40-60:0.01-1 for blending; heating the blend above its melting point while evacuating; obtaining PET-liquid crystal polymer copolymer after 2-8 hours;
(2) adding PET, a liquid crystal polymer and a PET-liquid crystal polymer copolymer into a high-speed mixer, and mixing for 3-5 minutes at normal temperature to obtain a mixture;
(3) adding the mixture into a double-screw extruder, fully melting and mixing to obtain a blend melt, and extruding and granulating to obtain in-situ composite polyester; the working temperature of the extruder was: 230 +/-5 ℃ in the first zone, 240 +/-5 ℃ in the second zone, 260 +/-5 ℃ in the third zone, 275 +/-5 ℃ in the fourth zone, 285 +/-5 ℃ in the fifth zone, 290 +/-5 ℃ in the sixth zone and 285 +/-5 ℃ in the seventh zone.
3. The method of preparing an extrudable film-forming liquid crystalline polymer/PET in situ composite polyester material as claimed in claim 2, wherein: the catalyst used is selected from the group consisting of the conventional basic catalysts and acidic catalysts.
4. The method of preparing an extrudable film-forming liquid crystalline polymer/PET in situ composite polyester material as claimed in claim 2, wherein: the alkaline catalyst is selected from potassium hydroxide, sodium methoxide and organic amine; the acidic catalyst is selected from concentrated sulfuric acid, sulfonic acid or a mixture thereof, phosphates, zirconium sulfate, tin sulfate, zirconium oxide and zirconium tungstate.
5. A film, characterized by: it is prepared from the liquid crystal polymer/PET in-situ composite polyester as claimed in any one of claims 1-4 by extrusion blow molding or extrusion biaxial stretching molding method.
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