CN1436811A - Prepn process of in-situ compound thermal liquid crystal polyester material with both fireproof and reinforcing performance - Google Patents
Prepn process of in-situ compound thermal liquid crystal polyester material with both fireproof and reinforcing performance Download PDFInfo
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- CN1436811A CN1436811A CN 02113315 CN02113315A CN1436811A CN 1436811 A CN1436811 A CN 1436811A CN 02113315 CN02113315 CN 02113315 CN 02113315 A CN02113315 A CN 02113315A CN 1436811 A CN1436811 A CN 1436811A
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Abstract
The present invention discloses the preparation process of in-situ compounded thermal liquid crystal polyester material with both fireproof and reinforcing performance. The preparation process may be one of adding polynary copolyester containing fireproof element and liquid crystal element simultaneously into polyethylene glycol terephthalate base material on the basis of conventional solution blending or melting blending process. The composite material thus prepared has both high fireproof efficiency and high mechanical performance. The present invention expands the application of polyester material in fireproof field.
Description
One, technical field
The invention belongs to the preparing technical field of flame retardant products, be specifically related to a kind of preparation and have fire-retardant simultaneously and method enhanced thermotropic liquid crystalline polyester in-situ composite.
Two, background technology
Polyethylene terephthalate (PET) is because its breaking tenacity and Young's modulus height, and Heat stability is good is fast light, weathering resistance is all good, makes it to become a kind of broad-spectrum thermoplastic macromolecule material, as fiber, engineering plastics, wrapping material etc.But, the same with most of organic polymer materials, because its oxygen index is lower, have only 20～22, flammable high, thereby limited it in the fire retardant material Application for Field.In order to change this present situation, traditional way is that the fire retardant that adds addition type in polyethylene terephthalate carries out blending and modifying.Though this method can improve the flame retardant properties of polyethylene terephthalate, but because conventional simple additive flame retardant, as halogen containing flame-retardant, inorganic combustion inhibitor etc. with poly-to dioctyl phthalate glycol ester difference structurally, the consistency of co-mixing system is poor, micron-scale phase separation takes place easily, thereby destroys the excellent mechanical property that pet material itself has.In this case, be glass enhanced words if take with traditional macroscopic fiber, the viscosity of one side meeting raising system in the course of processing, cause mobile decline, the processibility variation also can be brought wearing and tearing to equipment on the other hand in the course of processing, shorten the work-ing life of equipment.Thereby, how to solve the flame retardant resistance of pet material and the contradiction between the mechanical property, be to expand it in flame retardant area, to use the spatial key.
Three, summary of the invention
Task of the present invention is to solve the problem that prior art exists, and providing a kind of can preparation have fire-retardant and method enhanced thermotropic liquid crystalline polyester in-situ composite simultaneously.
As everyone knows, thermic Wholly aromatic liquid-crystalline copolyesters itself has good mechanical performance and processing characteristics, when itself and thermal plasticity high polymer form in-situ composite, just can give matrix material outstanding mechanical property (G.Kiss, Polym.Eng.Sci., 1987,27:410), if also contain ignition-proof element therein, will obtain flame retardant resistance simultaneously obviously.Principle of the present invention is exactly to make polyethylene terephthalate obtain higher flame retardant resistance again when improving its mechanical property by the thermic Wholly aromatic liquid-crystalline copolyesters that adding contains ignition-proof element.
The concrete technology that preparation method provided by the invention adopts both can be conventional solution blended process or melt-blending process, if employing melt-blending process, its technology is vacuum-drying → mechanically mixing → melting mixing and extrudes → drawing-off → cooling and dicing, and the feature of the inventive method is to make base material with polyethylene terephthalate, adds the multicomponent copolyester blend that contains ignition-proof element and liquid crystal unit simultaneously therein and is prepared.Because this multicomponent copolyester is the thermotropic liquid crystal superpolymer, in the melt-processed process, easily in field of flow, take place to be orientated and original position formation fento, be dispersed in the base material of polyethylene terephthalate, bring into play its inherent rigidity and intensity, play enhancement.Secondly also contain ignition-proof element in this multicomponent copolyester, so utilize the inventive method can obtain to have simultaneously fire-retardant and thermotropic liquid crystalline polyester in-situ composite reinforced effects.
In preparation method provided by the invention, it fills a prescription by mass percentage, and the addition of polyethylene terephthalate is 70～98%, the addition of multicomponent copolyester is 2～30%, and wherein the ignition-proof element that multicomponent copolyester contained can be phosphorus, nitrogen, sulphur, preferred phosphoric.Because the flame retardant effect of phosphoric is than the good flame retardation effect of other ignition-proof element, smoke-suppressing is strong, and can not emit poisonous or corrosive gases in combustion processes.And multicomponent copolyester specifically is by the phosphorous bifunctional compound that has the phenanthrene ring structure on the side group and contains the aromatic series bifunctional compound of carboxyl and contain carboxyl or/and the aromatic series bifunctional compound of hydroxyl forms through the esterification of routine.
Have on the wherein added side group the phosphorous bifunctional compound of phenanthrene ring structure can be preferably following any:
Contain the aromatic series bifunctional compound of carboxyl can be preferably following any:
The aromatic series bifunctional compound that contains carboxyl and hydroxyl or hydroxyl then can be preferably following any:
The present invention has the following advantages:
1, adopts method provided by the invention can solve the flame retardant resistance of pet material in traditional flame-retarded technology and the contradiction between the mechanical property, expanded its application space in flame retardant area.
2, can prepare flame retardant resistance and all good polyester in-situ composite of mechanical property with the inventive method, and the good good workability that is brought of component compatibility, make it adopt conventional method can carry out aftershaping processing.
3, owing to polyester in-situ composite with the inventive method preparation, its wild phase is the fento that thermotropic liquid crystal high polymer forms, thereby material just can eliminate friction, the wearing and tearing that traditional glass fibre reinforced composite material brings equipment in the reprocessing process, prolonged the work-ing life of contour machining equipment.
4, it is simple to prepare polyester in-situ composite technology with the inventive method, is easy to control.
Four, description of drawings
Provide the electron scanning micrograph in the polyester in-situ composite transverse section that is the inventive method preparation in the accompanying drawing.
Five, embodiment
Be that example provides embodiment with melt blending technology below, so that the present invention is carried out concrete description, but the present invention is not limited to following examples, and the person skilled in the art in this field can do some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1～5
(1) vacuum-drying is by the polyethylene terephthalate of each listed embodiment of table 1 with contain the proportioning of the multicomponent copolyester of ignition-proof element and liquid crystal unit simultaneously, material is put into vacuum drying oven respectively, 70～90 ℃ drying is more than 20 hours down in vacuum tightness 0.1～10mmHg, temperature, and control water ratio 0.5～5% is advisable.
(2) material of mechanically mixing after with vacuum-drying put into the high speed rotating device and mixed.
(3) melting mixing is extruded and the material that mixes is put into common double screw extrusion press melt blending is extruded.The temperature of each section of forcing machine is controlled to be 235 ℃, 250 ℃, 280 ℃, 295 ℃, 280 ℃, 280 ℃, 270 ℃ respectively, and head temperature is 260 ℃, 20～50 rev/mins of extruder screw rotating speeds.
(4) the material bar that will extrude of drawing-off carries out drawing-off under normal temperature air, ratio of drawing control 1～10.
(5) to put into temperature be that 10～25 ℃ water-bath is cooled off to the material bar of cooling and dicing after with drawing-off, and pelletizing gets final product then.
Flame retardant resistance and mechanical property for the polyester in-situ composite of investigating the present invention preparation, we are placed on the matrix material vacuum-drying of gained in the injection moulding machine, and polyester Shooting Technique condition routinely is injection molded into 130 * 6.5 * 3 millimeters standard batten and has carried out the test of following performance.
1, oxygen index test
Press the method test of GB2400-80 regulation with JF-3 type oxygen index instrument.
2, tensile property test
With the test of WD-5 electronic universal experimental machine, 50 millimeters/minute of rates of extension.
Table 2 is polyester in-situ composite and the combustionproperty of pure polyester and the contrast of tensile property of the present invention's preparation.
Also adopt scanning electronic microscope that the fracture morphology of prepared polyester in-situ composite is observed in addition, the results are shown in accompanying drawing.Photo shows microfibrillar structure formation in the accompanying drawing.
Table 1
Table 2
| Embodiment | Polyethylene terephthalate (%) | The multicomponent copolyester (%) that contains ignition-proof element and liquid crystal unit simultaneously |
| ????1 | ????95 | ????5 |
| ????2 | ????90 | ????10 |
| ????3 | ????85 | ????15 |
| ????4 | ????80 | ????20 |
| ????5 | ????70 | ????30 |
| Description of materials | Oxygen index (%) | Tensile strength (MPa) |
| Pure polyester | ????21.8 | ????260 |
| The polyester in-situ composite | ????38.2 | ????400 |
Claims (5)
1, a kind of have preparation method fire-retardant and enhanced thermotropic liquid crystalline polyester in-situ composite simultaneously, its technology can be solution blended process or melt-blending process, it is characterized in that this method is to add the multicomponent copolyester that contains ignition-proof element and liquid crystal unit simultaneously to carry out the blend preparation in the polyethylene terephthalate base material.
2, according to claim 1 have preparation method fire-retardant and enhanced thermotropic liquid crystalline polyester in-situ composite simultaneously, the prescription that it is characterized in that this method addition of polyethylene terephthalate by mass percentage is 70～98%, and the addition of multicomponent copolyester is 2～30%.
3, according to claim 1 and 2 have preparation method fire-retardant and enhanced thermotropic liquid crystalline polyester in-situ composite simultaneously, it is characterized in that the ignition-proof element that multicomponent copolyester contains is a phosphoric.
4, according to claim 1 and 2 have preparation method fire-retardant and enhanced thermotropic liquid crystalline polyester in-situ composite simultaneously, it is characterized in that multicomponent copolyester be by the phosphorous bifunctional compound that has the phenanthrene ring structure on the side group and contain the aromatic series bifunctional compound of carboxyl and contain carboxyl or/and the aromatic series bifunctional compound of hydroxyl through esterification and multicomponent copolyester.
5, according to claim 3 have preparation method fire-retardant and enhanced thermotropic liquid crystalline polyester in-situ composite simultaneously, it is characterized in that multicomponent copolyester be by the phosphorous bifunctional compound that has the phenanthrene ring structure on the side group and contain the aromatic series bifunctional compound of carboxyl and contain carboxyl or/and the aromatic series bifunctional compound of hydroxyl through esterification and multicomponent copolyester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113315 CN1241986C (en) | 2002-02-04 | 2002-02-04 | Prepn process of in-situ compound thermal liquid crystal polyester material with both fireproof and reinforcing performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113315 CN1241986C (en) | 2002-02-04 | 2002-02-04 | Prepn process of in-situ compound thermal liquid crystal polyester material with both fireproof and reinforcing performance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1436811A true CN1436811A (en) | 2003-08-20 |
| CN1241986C CN1241986C (en) | 2006-02-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02113315 Expired - Lifetime CN1241986C (en) | 2002-02-04 | 2002-02-04 | Prepn process of in-situ compound thermal liquid crystal polyester material with both fireproof and reinforcing performance |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134495A (en) * | 2010-12-30 | 2011-07-27 | 金发科技股份有限公司 | High-fluidity liquid crystal polymer composition and preparation method thereof |
| CN102807666A (en) * | 2011-05-31 | 2012-12-05 | 三星电机株式会社 | Insulating resin composition used for printed circuit board (PCB) and PCB comprising the same |
| CN106917192A (en) * | 2017-03-31 | 2017-07-04 | 中原工学院 | A kind of preparation method of fireblocking nonwoven cloth |
| CN112608461A (en) * | 2020-12-17 | 2021-04-06 | 上海思涛新材料科技有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof |
-
2002
- 2002-02-04 CN CN 02113315 patent/CN1241986C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134495A (en) * | 2010-12-30 | 2011-07-27 | 金发科技股份有限公司 | High-fluidity liquid crystal polymer composition and preparation method thereof |
| CN102807666A (en) * | 2011-05-31 | 2012-12-05 | 三星电机株式会社 | Insulating resin composition used for printed circuit board (PCB) and PCB comprising the same |
| CN106917192A (en) * | 2017-03-31 | 2017-07-04 | 中原工学院 | A kind of preparation method of fireblocking nonwoven cloth |
| CN112608461A (en) * | 2020-12-17 | 2021-04-06 | 上海思涛新材料科技有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof |
| CN112608461B (en) * | 2020-12-17 | 2021-08-17 | 上海思涛新材料科技有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1241986C (en) | 2006-02-15 |
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