CN104098760A - Method for inhibiting self-polymerization of PABA in preparation of thermally-induced PET-PHB liquid crystal polyester - Google Patents
Method for inhibiting self-polymerization of PABA in preparation of thermally-induced PET-PHB liquid crystal polyester Download PDFInfo
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Abstract
The invention relates to a method for inhibiting self-polymerization of PABA in preparation of thermally-induced PET-PHB liquid crystal polyester. The method includes following steps: adding p-hydroxybenzoic acid and polyethylene glycol terephthalate, as raw material monomers, to an acetic anhydride solvent with addition of a catalyst in the acetic anhydride solvent; carrying out an acetylation reaction to obtain a solution; adding CH3COOH to carry out an ester exchange reaction and a condensation polymerization reaction to obtain a polyester-type thermally-induced liquid crystal polymer PET/PHB. A synthetic technology with addition of CH3COOH is employed in the invention. The prepared PET-PHB thermally-induced liquid crystal polyester is uniform in structure, low in a melting point, high in molecular weight and modulus and excellent in moulding machinability. In addition, the method is simple in operation, is short in a process period, can be completed in general equipment, can replace conventional metal, ceramic, thermosetting materials and other high-performance thermoplastic materials, and is importantly applied in high-tech technical fields such as electronic technology, information, communication, aerospace and the like and industrial fields such as automobile, machinery, chemistry, medical treatment and the like.
Description
Technical field
The invention belongs to the preparation technology field of PET/PHB thermotropic liquor polyester, particularly a kind of preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester.
Background technology
Liquid crystal polymer (Liquid Crystal Polymer, be called for short LCP) be the class novel high polymer material developing rapidly nearest decades, it is not only that polymer science and liquid crystal science are intersected mutually and the brand-new research field that forms, and there is unique structure and excellent performance, impel people more carefully to go to investigate its characteristic, synthetic there is the more liquid crystal high polymer material of novel structure, be more described as in the world in recent years " novel material of 21 century " or " Super Engineering material ".Liquid crystal polymer (LCP) is the polymer that can exist with liquid crystal phase under certain condition.Compared with other polymer, liquid crystal polymer has mesomorphic phase special molecular orientation order and position-order; Compared with small molecules liquid crystalline cpd, liquid crystal polymer has again high molecular characteristic.The combination of polymer and liquid crystal phase sequence has been given liquid crystal polymer with distinct individual character and characteristic, and as the brand-new high performance material of a class, liquid crystal polymer is in modern high-tech field future.
PET/PHB multipolymer is to report the earliest the polymer with thermotropic liquid crystal, it has high strength and high-modulus, the outstanding excellent properties such as minimum, the good melt processable of thermotolerance, linear expansivity, good mechanical property, and taking not too expensive PHB and inexpensive PET as basic raw material, be the thermotropic liquid crystal high polymer of being familiar with the earliest, given PET/PHB multipolymer very large incentive.Eastman Kodak Co has also made commodity Polyester X7G accordingly.Such preparation method has the even possibility of homopolymer of the PHB homopolymerization segment of generation, makes the control ratio of molecular chain chemical structure more difficult, all the more so in the time that PHB input amount is higher especially.One of important consequence of PET/PHB copolymer chain ununiformity, the heat-drawn wire that is material is lower, another important consequence of copolymer chain ununiformity is that the crystallization of being rich in PHB long-chain section is extruded (extrusion temperature generally at 225-285 DEG C) without fusing because fusing point is too high in melt-processed process, has hindered the reorientation of molecular chain in extrusion.This limit the reinforced effects of PHB composition to copolyesters, also caused the waste of PHB simultaneously.
Japan Unitika Ltd. improves the polymerization process of Eastman Kodak company, become and once feed intake as step feeding, to reduce the concentration of PHB monomer in polymerization system and the chance of self condensation, make the atactic polyester PET/PHB of high PHB content, and release Rodrun LC-5000 series product (Suenaga the end of the eighties, 1988,1990).But, these methods
[1～6]all do not consider the engineering problem that PET/PHB liquid crystal copolyester is synthetic, large absolutely number all adopts 2 footworks, first PHB acetylize is made to PABA, and then carries out transesterification reaction with PET.This method is wasted very large in the time of purification PABA, and yield is very low, industrial can not employing.
Up to now, about there is not yet pertinent literature and patent report preparing the processing method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester, and the present invention adopts and adds CH
3the synthesis technique of COOH, prepares gained PET/PHB TLCP even structure, and fusing point is low, and molecular weight is high, high strength and high-modulus, and forming process is good; And preparation method is simple to operate, process cycle is short, can in general-purpose equipment, complete, metal, pottery, thermosetting material and other high performance thermoplastic material of the alternative original use of this PET/PHB thermotropic liquid crystalline polyester, and obtained important application at industrial sectors such as the high-technology fields such as electronics, information, communication, aerospace and automobile, machinery, chemical industry and medical treatment.
Of the present invention a kind of preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester, comprising:
Add in acetic anhydride solvent taking P-hydroxybenzoic acid PHB and lower molecular weight polyethylene terephtalate (η inh is as 0.2～0.4dL/g) as starting monomer, and add catalyzer in acetic anhydride solvent, first carry out acetylization reaction, then add CH3COOH to carry out transesterify, polycondensation, when 80%～85% by product acetic acid steams, when controlling the viscosity of reaction system and increasing to η inh and be 0.2～0.4dL/g, stop logical nitrogen, start to vacuumize, blowing after continuation reaction 2～5h under vacuum tightness 0～200Pa, the synthetic polyester type TLCP PET/PHB that makes.
The mol ratio of described P-hydroxybenzoic acid PHB and lower molecular weight polyethylene terephtalate is 30:70～70:30;
The mol ratio of described P-hydroxybenzoic acid PHB and acetic anhydride solvent is 0.2～0.8:1;
Any acetate and the composite catalyst forming containing the compound of antimony in described catalyzer chosen from Fe, calcium, antimony, zinc or tin, the mol ratio of catalyzer and PHB is 0.0005～0.005:1;
Described CH
3the mol ratio of COOH and P-hydroxybenzoic acid PHB is 1～8:1, and preferred mol ratio is 5～6:1;
The temperature of reaction of described acetylization reaction is 100 DEG C～150 DEG C, reaction times 0.5h～3h;
Described transesterify, polycondensation is under nitrogen protection, to be rapidly heated to 270～290 DEG C, reaction 4～10h.
Conventionally the two-step process adopting, the first step is that PHB and acetic anhydride are first carried out to acetylization reaction generation PABA, and this PABA is carried out to purification; Second step, carries out polycondensation by refined PABA and PET.There is the difficulty of PABA purification in this technique, process cycle is long, and condensation polymerization speed is slow, self-aggregate (IV) in the middle of easily producing, and the viscosity of the liquid crystal polyester obtaining is low.
Compared with conventional two-step approach; thereby only need the polycondensation phase after acetylize finishes adding a certain amount of CH3COOH, the present invention obtains the liquid crystalline polymers of even structure to suppress the autohemagglutination of PABA; through the synthetic polyester type TLCP PET/PHB for preparing of single stage method; not only can shorten process cycle; accelerate speed of reaction; and can suppress the autohemagglutination of PABA by adding acetic acid, can obtain the PET/PHB thermotropic liquid crystalline polyester of even structure, material mechanical performance excellence.
Beneficial effect
(1) the present invention adopts and adds CH
3the synthesis technique of COOH, prepares gained PET/PHB TLCP even structure, fusing point low (being 200 DEG C), molecular weight high (up to 1.0), limiting viscosity η
inhbe 0.3～1.0dL/g, high strength and high-modulus, forming process is good;
(2) this preparation method is simple to operate, and process cycle is short, can in general-purpose equipment, complete, and has good economic benefits and industrial applications prospect;
(3) metal of the alternative original use of PET/PHB thermotropic liquid crystalline polyester of the present invention, pottery, thermosetting material and other high performance thermoplastic material, and obtained important application at industrial sectors such as the high-technology fields such as electronics, information, communication, aerospace and automobile, machinery, chemical industry and medical treatment.
Brief description of the drawings
Fig. 1 is that PET/PHB thermotropic liquid crystalline polyester POM prepared by embodiment 1 analyzes collection of illustrative plates;
Fig. 2 is that PET/PHB thermotropic liquid crystalline polyester POM prepared by embodiment 2 analyzes collection of illustrative plates;
Fig. 3 is that PET/PHB thermotropic liquid crystalline polyester POM prepared by embodiment 3 analyzes collection of illustrative plates;
Fig. 4 is that PET/PHB thermotropic liquid crystalline polyester POM prepared by embodiment 4 analyzes collection of illustrative plates;
Fig. 5 is that PET/PHB thermotropic liquid crystalline polyester POM prepared by embodiment 5 analyzes collection of illustrative plates;
Fig. 6 is that PET/PHB thermotropic liquid crystalline polyester POM prepared by comparative example 1 analyzes collection of illustrative plates;
Fig. 7 is that PET/PHB thermotropic liquid crystalline polyester POM prepared by comparative example 2 analyzes collection of illustrative plates;
Fig. 8 is that PET/PHB thermotropic liquid crystalline polyester POM prepared by comparative example 3 analyzes collection of illustrative plates.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Analysis test method is as follows:
1. Viscosity Analysis
Adopt Ubbelohde viscometer to analyze, phenol taking mass ratio as (50:50), the mixed solution of tetrachloroethane, as solvent, are made into 0.5%(w%) the limiting viscosity viscosities il inh of the solution determination of ubbelohde viscometer PET/PHB liquid crystal polyester that is 0.7～0.8mm by capillary diameter at 25 ± 0.1 DEG C.
Calculation formula:
2. polarized microscope analysis
Adopt polarizing microscope (POM) that PET/PHB liquid crystal copolyester is cut into slices and analyzed, by observing the form that has liquid crystal in temperature-rise period and temperature-fall period, the BX51 type polarizing microscope that analytical instrument is OLYMPUS.
Embodiment 1
By 55.5g(0.402mol) PHB, 179.8g(0.934mol) lower molecular weight PET (η inh is 0.2～0.4dL/g), 163.2g(1.57mol) AC
2o and containing zinc acetate 0.042g(2.2 × 10
-4and Sb mol)
2o
30.00316g(1.09 × 10
-4mol) composite catalyst joins in the reactor of 2L acetylize 2h at 150 DEG C together; after acetylize finishes, add 125.7ml(2.09mol) CH3COOH; be rapidly heated to 280 DEG C and carry out transesterify, polycondensation 6～8 hours; steam 80%-85% by product acetic acid, the viscosity of controlling reaction system increases to η
inhwhile being 0.2～0.4dL/g, stop logical nitrogen, start to vacuumize, and after low vacuum is to continue reaction 3h under 0～200Pa blowing.The product obtaining is carried out to limiting viscosity analysis, and measuring viscosity is that 0.506dL/g(is as shown in table 1), and the product compressing tablet that takes a morsel carries out POM analysis, as shown in Figure 1, liquid crystal liquid crystal property is not obvious.
Embodiment 2
By 83.25g(0.603mol) PHB, 174.21g(0.950mol) lower molecular weight PET (η inh is 0.2～0.4dL/g), 244.8g(2.38mol) AC
2o and containing zinc acetate 0.0603g (3.29 × 10
-4and Sb mol)
2o
30.00474g(1.635 × 10
-4mol) composite catalyst joins in the reactor of 2L acetylize 2h at 150 DEG C together, adds 188ml(3.14mol after acetylize finishes) CH
3cOOH, is rapidly heated to 280 DEG C and carries out transesterify, polycondensation 6～8 hours, steams 80%-85% by product acetic acid, and the viscosity of controlling reaction system increases to η
inhwhile being 0.2～0.4dL/g, stop logical nitrogen, start to vacuumize,, and after low vacuum is to continue reaction 3h under 0～200Pa blowing.The product obtaining is carried out to limiting viscosity analysis, and measuring viscosity is that 0.40dL/g(is as shown in table 1), and the product compressing tablet that takes a morsel carries out POM analysis, as shown in Figure 2, can find out that product has a small amount of black and white schlieren shape striped.
Embodiment 3
By 88.25g(0.603mol) PHB, 116.1g(0.603mol) lower molecular weight PET (η inh is 0.2～0.4dL/g), 244.8g(2.38mol) AC
2o and containing zinc acetate 0.0603g (3.29 × 10
-4and Sb mol)
2o
30.00474g(1.635 × 10
-4mol) composite catalyst joins in the reactor of 2L acetylize 2h at 150 DEG C together, adds 188ml(3.14mol after acetylize finishes) CH
3cOOH, is rapidly heated to 280 DEG C and carries out transesterify, polycondensation 6～8 hours, steams 80%-85% by product acetic acid, and the viscosity of controlling reaction system increases to η
inhwhile being 0.2～0.4dL/g, stop logical nitrogen, start to vacuumize,, and after low vacuum is to continue reaction 3h under 0～200Pa blowing.The product obtaining is carried out to limiting viscosity analysis, and measuring viscosity is that 0.567dL/g(is as shown in table 1), and the product compressing tablet that takes a morsel carries out POM analysis, as shown in Figure 3, can find out that product has obvious colored shadow shape striped.
Embodiment 4
By 110.4g(0.799mol) PHB, 102.4g(0.532mol) lower molecular weight PET (η inh is 0.2～0.4dL/g), 326.4g(3.17mol) AC
2o and containing zinc acetate 0.0799g(4.36 × 10
-4and Sb mol)
2o
30.00628g(2.166 × 10
-4mol) composite catalyst joins in the reactor of 2L acetylize 2h at 150 DEG C together, adds 250ml(4.17mol after acetylize finishes) CH
3cOOH, is rapidly heated to 280 DEG C and carries out transesterify, polycondensation 6～8 hours, steams 80%-85% by product acetic acid, and the viscosity of controlling reaction system increases to η
inhwhile being 0.2～0.4dL/g, stop logical nitrogen, start to vacuumize,, and after low vacuum is to continue reaction 3h under 0～200Pa blowing.The product obtaining is carried out to limiting viscosity analysis, and measuring viscosity is that 0.796dL/g(is as shown in table 1), and the product compressing tablet that takes a morsel carries out POM analysis, as shown in Figure 4, can find out that product has very strong colour schlieren shape striped
Embodiment 5
By 138.0g(1.00mol) PHB, 82.54g(0.429mol) lower molecular weight PET (η inh is 0.2～0.4dL/g), 408.0g(3.97mol) AC
2o and containing zinc acetate 0.1g(5.46 × 10
-4and Sb mol)
2o
30.00786g(2.711 × 10
-4mol) composite catalyst joins in the reactor of 2L acetylize 2h at 150 DEG C together, adds 312ml(5.21mol after acetylize finishes) CH
3cOOH, is rapidly heated to 280 DEG C and carries out transesterify, polycondensation 6～8 hours, steams 80%-85% by product acetic acid, and the viscosity of controlling reaction system increases to η
inhwhile being 0.2～0.4dL/g, stop logical nitrogen, start to vacuumize,, and after low vacuum is to continue reaction 3h under 0～200Pa blowing.The product obtaining is carried out to limiting viscosity analysis, and measuring viscosity is that 0.965dL/g(is as shown in table 1), and the product compressing tablet that takes a morsel carries out POM analysis, as shown in Figure 5, can find out that product has very strong colour schlieren shape striped.
Comparative example 1
By 108.6g(0.603mol) PABA, 116.1g(0.603mol) lower molecular weight PET (η inh is 0.2～0.4dL/g), catalyst S b
2o
30.00474g(1.635 × 10
-4mol) join together in the reactor of 2L in 280 DEG C and carry out transesterify, polycondensation 6～8 hours, steam 80%-85% by product acetic acid, the viscosity of controlling reaction system increases to η
inhwhile being 0.2～0.4dL/g, stop logical nitrogen, start to vacuumize, and after low vacuum is to continue reaction 3h under 0～200Pa blowing.The product obtaining is carried out to limiting viscosity analysis, and measuring viscosity is that 0.567dL/g(is as shown in table 1), and the product compressing tablet that takes a morsel carries out POM analysis, as shown in Figure 6, can find out that product has obvious colored shadow shape striped.
Comparative example 2
By 143.9g(0.799mol) PABA, 102.4g(0.532mol) lower molecular weight PET (η inh is 0.2～0.4dL/g), catalyst S b
2o
30.00628g(2.166 × 10
-4mol) join together in the reactor of 2L in 280 DEG C and carry out transesterify, polycondensation 6～8 hours, steam 80%-85% by product acetic acid, the viscosity of controlling reaction system increases to η
inhwhile being 0.2～0.4dL/g, stop logical nitrogen, start to vacuumize, and after low vacuum is to continue reaction 3h under 0～200Pa blowing.The product obtaining is carried out to limiting viscosity analysis, and measuring viscosity is that 0.567dL/g(is as shown in table 1), and the product compressing tablet that takes a morsel carries out POM analysis, as shown in Figure 7, can find out that product has obvious colored shadow shape striped.
Comparative example 3
By 180.16g(1.00mol) PABA, 82.54g(0.429mol) lower molecular weight PET (η inh is 0.2～0.4dL/g), catalyst S b
2o
30.00786g(2.711 × 10
-4mol) join together in the reactor of 2L in 280 DEG C and carry out transesterify, polycondensation 6～8 hours, steam 80%-85% by product acetic acid, the viscosity of controlling reaction system increases to η
inhwhile being 0.2～0.4dL/g, stop logical nitrogen, start to vacuumize, and after low vacuum is to continue reaction 3h under 0～200Pa blowing.The product obtaining is carried out to limiting viscosity analysis, and measuring viscosity is that 0.567dL/g(is as shown in table 1), and the product compressing tablet that takes a morsel carries out POM analysis, as shown in Figure 8, can find out that product has obvious colored shadow shape striped.
Different process, proportioning raw materials molecular weight, the viscosity to PET/PHB liquid crystal polyester, liquid crystal liquid crystal property all has impact.Particular case is shown in embodiment, following subordinate list 1.
Table 1 is the inhomogeneity impact on PET/PHB liquid crystal polyester viscosity and liquid crystal liquid crystal property and structure of the composition of raw material
Note: embodiment 1～5 is single stage method (adding acetic acid) synthesis technique, and comparative example 1～3 is two step synthesis technique
The PET/PHB liquid crystal polyester of synthesized of the present invention as can be seen from Table 1, adopts single stage method better than two-step approach, and the composition of raw material is very large on product viscosity (molecular weight) impact.In the time that PET/PHB mol ratio is 70:30, synthetic liquid crystal polyester viscosity maximum.When PET/PHB mol ratio is greater than 50:50, the liquid crystal liquid crystal property of the liquid crystal polyester obtaining is fine, with respect to two-step approach, adds CH
3the uniform liquid crystal polyester of single stage method energy composite structure of COOH, can well suppress the autohemagglutination of acetylate PABA.
Although the present invention discloses preferred embodiment as above; so it is not in order to limit content of the present invention; anyly be familiar with this skill person; not departing from main spirits of the present invention and context; when doing various changes and retouching, therefore the protection domain of invention should be as the criterion with the basic right claimed range of applying for a patent.
Claims (10)
1. preparing a method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester, comprising:
Add in acetic anhydride solvent taking P-hydroxybenzoic acid PHB and lower molecular weight polyethylene terephtalate as starting monomer, and add catalyzer in acetic anhydride solvent, first carry out acetylization reaction, then add CH
3cOOH carries out transesterify, polycondensation, steams by product acetic acid, and the viscosity of controlling reaction system increases to η
inhwhile being 0.2～0.4dL/g, stop logical nitrogen, start to vacuumize, blowing after continuation reaction 2～5h under vacuum tightness 0～200Pa, the synthetic polyester type TLCP PET/PHB that makes.
2. according to claim 1 a kind of preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester, it is characterized in that: the mol ratio of described P-hydroxybenzoic acid PHB and lower molecular weight polyethylene terephtalate is 30:70～70:30.
3. according to claim 1 and 2 a kind of preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester, it is characterized in that: the η of described lower molecular weight polyethylene terephtalate
inhbe 0.2～0.4dL/g.
4. according to claim 1 a kind of preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester, it is characterized in that: the mol ratio of described P-hydroxybenzoic acid PHB and acetic anhydride solvent is 0.2～0.8:1.
5. according to claim 1 a kind of preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester, it is characterized in that: any acetate and the composite catalyst forming containing the compound of antimony in described catalyzer chosen from Fe, calcium, antimony, zinc or tin.
6. a kind of preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester according to claim 1 or 5, it is characterized in that: the mol ratio of catalyzer and PHB is 0.0005～0.005:1.
7. according to claim 1 a kind of preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester, it is characterized in that: the mol ratio of described CH3COOH and P-hydroxybenzoic acid PHB is 1～8:1.
8. according to claim 7 a kind of preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester, it is characterized in that: described CH
3the mol ratio of COOH and P-hydroxybenzoic acid PHB is 5～6:1.
9. according to claim 1 a kind of preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester, it is characterized in that: the temperature of reaction of described acetylization reaction is 100 DEG C～150 DEG C, reaction times 0.5h～3h.
10. according to claim 1 a kind ofly it is characterized in that: described transesterify, polycondensation is to be rapidly heated under nitrogen protection to 270～290 DEG C preparing the method that suppresses PABA autohemagglutination in thermic PET/PHB liquid crystal polyester, reaction 4～10h.
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|---|---|---|---|
| CN201310127297.3A CN104098760A (en) | 2013-04-12 | 2013-04-12 | Method for inhibiting self-polymerization of PABA in preparation of thermally-induced PET-PHB liquid crystal polyester |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860037A (en) * | 2016-02-01 | 2016-08-17 | 金发科技股份有限公司 | Liquid crystal polyester, molding composition composed of liquid crystal polyester and application of molding composition |
| CN105885369A (en) * | 2016-04-13 | 2016-08-24 | 珠海万通特种工程塑料有限公司 | Liquid crystal polyester composition |
| CN113150288A (en) * | 2021-04-21 | 2021-07-23 | 公牛集团股份有限公司 | Thermotropic liquid crystal high polymer and application thereof in PC resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0173752B1 (en) * | 1984-03-06 | 1989-02-22 | Mitsubishi Kasei Corporation | Process for producing melting-anisotropic, copolymerized polyester |
| JPH0627187B2 (en) * | 1985-02-05 | 1994-04-13 | 三菱化成株式会社 | Method for producing copolyester |
-
2013
- 2013-04-12 CN CN201310127297.3A patent/CN104098760A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0173752B1 (en) * | 1984-03-06 | 1989-02-22 | Mitsubishi Kasei Corporation | Process for producing melting-anisotropic, copolymerized polyester |
| JPH0627187B2 (en) * | 1985-02-05 | 1994-04-13 | 三菱化成株式会社 | Method for producing copolyester |
Non-Patent Citations (1)
| Title |
|---|
| 单国荣等: "PET/PHB液晶共聚酯的合成及液晶性能", 《合成树脂及塑料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860037A (en) * | 2016-02-01 | 2016-08-17 | 金发科技股份有限公司 | Liquid crystal polyester, molding composition composed of liquid crystal polyester and application of molding composition |
| CN105885369A (en) * | 2016-04-13 | 2016-08-24 | 珠海万通特种工程塑料有限公司 | Liquid crystal polyester composition |
| CN113150288A (en) * | 2021-04-21 | 2021-07-23 | 公牛集团股份有限公司 | Thermotropic liquid crystal high polymer and application thereof in PC resin |
| CN113150288B (en) * | 2021-04-21 | 2022-07-15 | 公牛集团股份有限公司 | Thermotropic liquid crystal high polymer and application thereof in PC resin |
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