CN103980674B - A kind of polyester powder and preparation method thereof of high inorganic content - Google Patents
A kind of polyester powder and preparation method thereof of high inorganic content Download PDFInfo
- Publication number
- CN103980674B CN103980674B CN201410181466.6A CN201410181466A CN103980674B CN 103980674 B CN103980674 B CN 103980674B CN 201410181466 A CN201410181466 A CN 201410181466A CN 103980674 B CN103980674 B CN 103980674B
- Authority
- CN
- China
- Prior art keywords
- polyester
- powder
- preparation
- mesh
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of polyester composite containing inorganic matter, includes the inorganic matter for leading to polyester shown in formula (I) and content is 75 weight % or more:
Description
Technical field
The present invention relates to a kind of 3D printing materials and preparation method thereof, and in particular to a kind of polyester powder material of high inorganic matter
Material and preparation method thereof.
Background technique
3D printing technique is also known as increases material manufacturing technology, it does not need traditional cutter, fixture and multi-step process, benefit
With three-dimensional design data it is automatic by process control on one device, rapidly and accurately produce the zero of arbitrarily complicated shape
Part designs and manufactures digitlization " freely manufacturing " to realize.Many complicated knots for being difficult to manufacture in the past may be implemented in the technology
The forming of structure part, and greatly reduce manufacturing procedure, shortens the process-cycle, is considered as that " one will change the skill in the world
Art " and cause global concern.Currently, 3D printing technique is gradually applied to medicine, bioengineering, clothes, building, space flight and aviation
Equal fields.
High molecular material has forming temperature is low, working power is small, forming accuracy is high etc. compared with metal, ceramic material
Advantage has become a kind of important 3D printing material.The type of 3D printing high molecular material mainly includes polystyrene, gathers
Amide, acrylonitrile-butadiene-styrene terpolymer and polylactic acid.However, relative to market-oriented high molecular weight species and
Speech, the high molecular material type that can be used for 3D printing is on the low side, causes the application range of current 3D printing product limited.This is because
That more or less there is mechanical strengths is low for conventional high molecular material, melt strength is low, heat distortion temperature is low, non-degradable etc. is asked
Topic.Therefore high molecular material novel, with preferable performance is developed to the significant of 3D printing technique.
Aromatic series saturated polyester, such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and poly-
Butylene terephthalate (PBT) etc. has preferable mechanical performance, hot property etc., is widely used in packaging, clothes, automobile
Etc. industries.
The method of modifying of inorganic powder filled polymer can not only be greatly lowered polymer material cost, but also can be with
Significantly improve the various performances of polymer material, such as mechanical property, hot property and ageing properties.Due to inorganic matter and polymer
Poor compatibility, the problems such as polymer malt viscosity is big, the system of the polymer composites of high inorganic content (> 75 weight %)
It is standby extremely difficult.Carrying out modification of graft to inorganic powder surface is one of the most common process for improving inorganic content.But
This method process is cumbersome, it is difficult to large-scale industrial production.
Summary of the invention
The present invention provides a kind of polyester composite containing inorganic matter, includes:
Polyester shown in logical formula (I):
Wherein, Ar is phenyl, and two carboxyls replace on phenyl for contraposition or meta position；
The integer that m is 2 to 10；With
Content is the inorganic matter of 75 weight % or more.
In one embodiment, the n led in formula (I) is greater than 45 preferably 50 to 15000.
In one embodiment, the number-average molecular weight of the polyester is such as 1x104To 8x106, such as 2x104Extremely
5x106Or 4x104To 4x106Or 5x104To 3.5x106Or 6x104To 3x106g/mol。
In embodiments of the invention:
M can be such as 2,3,4,5,6,7,8,9 or 10, preferably 2,3,4,5 or 6, more preferable 2,3 or 4.
The content of inorganic matter preferably 75 to 98 weight %, such as 75 to 95 weight %.
The inorganic matter can be for for example selected from calcium carbonate, montmorillonite, attapulgite, kaolin, talcum powder, mica, nitrogen
Change one of boron, hexagonal boron nitride, stone powder, aluminum oxide, silica, titanium dioxide, carbon black, graphene or more
Kind.
In one embodiment, the intrinsic viscosity of the polyester is 0.55dL/g or more, such as 0.60 to 20.0dL/g.
In one embodiment, the polyester is polyethylene terephthalate, polytrimethylene terephthalate, poly- pair
Terephtha-late, polyethylene terephthalate, poly- M-phthalic acid propylene diester, one in poly- M-phthalic acid fourth diester
Kind is a variety of.
Preferably, the polyester material is the polyester composite powder by powder solid-phase tack producing.
The partial size of the polyester powder can be 2000 mesh hereinafter, such as 100 to 2000 mesh, for example, 150 mesh, 200 mesh,
250 mesh, 300 mesh, 350 mesh, 400 mesh, 450 mesh, 500 mesh, 550 mesh, 600 mesh, 700 mesh, 800 mesh, 900 mesh, 1000 mesh, 1100
Mesh, 1200 mesh, 1300 mesh, 1400 mesh, 1500 mesh, 1600 mesh, 1700 mesh, 1800 mesh, 1900 mesh.
The present invention also provides the preparation methods of the composite material, including powder solid-phase tack producing.
In one embodiment, the preparation method includes: injection mixing, crushing, screening and powder solid-phase tack producing.
Wherein, the injection mixing, crushing and screening include the following steps:
By low-viscosity polyester oligomer melt and inorganic matter by injection mixing, object crystallisation by cooling to be mixed and it is broken after,
The powder of oligomer coated inorganic object is obtained through air-flow crushing and screening.
Wherein, the powder sieved can be 2000 mesh hereinafter, such as 100~2000 mesh, for example, 150 mesh, 200 mesh,
250 mesh, 300 mesh, 350 mesh, 400 mesh, 450 mesh, 500 mesh, 550 mesh, 600 mesh, 700 mesh, 800 mesh, 900 mesh, 1000 mesh, 1100
Mesh, 1200 mesh, 1300 mesh, 1400 mesh, 1500 mesh, 1600 mesh, 1700 mesh, 1800 mesh, 1900 mesh.
The powder solid-phase tack producing can be heated by the multistage and be carried out, for example including the following steps:
1) powder of oligomer coated inorganic object is heated to 120~149 DEG C, keeps such as 1 to 8h；
2) by the resulting material raising temperature of step 1) to 150~189 DEG C, holding such as 2~for 24 hours；
3) by the resulting material raising temperature of step 2) to 190~220 DEG C, holding such as 2~for 24 hours, it is multiple to prepare polyester
Condensation material.
Wherein, step 1), 2) and/or 3) preferably carried out under conditions of nitrogen or high vacuum (being lower than 133Pa).
Preferably, the intrinsic viscosity of step 2) resulting material is 0.40~0.55dL/g.
It further include carrying out melt polycondensation before injection mixing in an embodiment of preparation method of the present invention.
The melt polycondensation includes the following steps:
1) in the presence of a catalyst, aromatic diacid Ar (COOH)2With glycol monomer HO (CH2)mOH, in catalyst
Under effect, polyester prepolyer is obtained by esterification or ester exchange reaction；Preferably, reaction temperature is 150~280 DEG C, instead
It is 1~5h between seasonable, system pressure is 40~500KPa；
2) for prepolymer under the action of polycondensation catalyst, vacuum polycondensation obtains low-viscosity polyester；Preferably, condensation temperature is
210~300 DEG C, system pressure is 0~500Pa, and the time is 0.5~10h.
Gained low-viscosity polyester intrinsic viscosity is 0.40dL/g hereinafter, for example, 0.10~0.40dL/g.
Wherein, the aromatic diacid Ar (COOH)2Can for such as terephthalic acid (TPA), dimethyl terephthalate (DMT),
Phthalic acid and/or dimethyl isophthalate.
HO- (the CH2)m- OH monomer can be such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, heptan two
Alcohol, ethohexadiol, nonanediol, decanediol, preferably ethylene glycol, propylene glycol, butanediol, pentanediol and hexylene glycol, most preferably ethylene glycol,
Propylene glycol and butanediol.
The present invention also provides the printed materials comprising polyester composite of the present invention, especially 3D printing material.
The present invention also provides polyester composites of the present invention to be used to prepare printed material, the especially use of 3D printing material
On the way.
The beneficial effect comprise that
1, it by the flow of polyester oligomer melt and inorganic particle in control injection mixed process, can prepare high inorganic
Inorganic matter/polyester complexes of object content, and inorganic matter is uniformly dispersed；
2, for the inorganic material powders material of gained polyester cladding after 3D printing shapes, preparation has mechanical strength high, hot
The features such as deformation temperature is high；
3, production process of the present invention is simple, easy to industrialized production.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Intrinsic viscosity is measured as follows in following embodiments:
Intrinsic viscosity (I.V.): 0.1250g polyester is dissolved in the phenol and 1,1,2,2- tetrachloroethanes mixed solvent (weight of 25ml
Amount compares in 1/1), is measured in 25 ± 0.1 DEG C of thermostat with Ubbelohde viscometer.
The preparation of 1 talcum powder of embodiment/polyethylene terephthalate composite powder
3.00Kg terephthalic acid (TPA), 1.52Kg ethylene glycol are put into 10L batch condensation polymerization reactor, 1.21g antimony glycol heats up and adds
Pressure is esterified, and 200~240 DEG C of temperature, pressure is not higher than 350KPa.Water is distilled out of simultaneously for esterification, and the water to theoretical amount is removed
After going, polycondensation reaction is carried out.After reaching 270 DEG C to polycondensation vessel temperature, carry out polycondensation reaction, system temperature control are vacuumized
At 270~280 DEG C, pressure < 50Pa.When polycondensation vessel stirring motor revolution is 25Hz, discharging when electric current reaches 86mA obtains PET
Oligomer, measuring intrinsic viscosity is 0.28dL/g.
Gained PET oligomer melt and the talcum powder (talc) of 1000 mesh are after injection mixes, through crusher and pulverizer
It after crushing (60~100 mesh), then is further crushed through airslide disintegrating mill, sieves collection cut size in 150~250 mesh powders.
Powder solid-phase tack producing: the powder of low viscous PET cladding talc is placed in 10L rotary drum, heating up and vacuumizing makes material
Sufficient crystallising, temperature are 140 DEG C, pressure < 50Pa, time 5h；Heating carries out preliminary thickening and reacts and crystallize material further,
Temperature is 185 DEG C, time 8h；It further heats up to 215 DEG C, time 8h, discharges.
In gained powder-product, PET viscosity is 18.5dL/g, and the corresponding equal relative molecular weight of number is 2.56 × 106G/mol,
Talc content is 82 weight %.
The preparation of 2 calcium carbonate of embodiment/polyethylene terephthalate composite powder
Investment 2.50Kg dimethyl terephthalate (DMT) in 10L batch condensation polymerization reactor, 1.65Kg ethylene glycol, 0.57g zinc acetate,
0.59g antimony oxide, heating progress transesterification, 160~210 DEG C of temperature.Methanol is distilled out of simultaneously for transesterification, to theoretical amount
After methanol is removed, polycondensation reaction is carried out.After reaching 270 DEG C to polycondensation vessel temperature, carry out polycondensation reaction, system are vacuumized
Temperature control is at 270~280 DEG C, pressure < 50Pa.When polycondensation vessel stirring motor revolution be 25Hz, discharging when electric current reaches 94mA,
Measuring intrinsic viscosity is 0.31dL/g.
Gained PET oligomer melt and the calcium carbonate of 2000 mesh are after injection mix, after crusher and pulverizer crushing
(60~100 mesh), then further crushed through airslide disintegrating mill, collection cut size is sieved in 250~500 mesh powders.
Powder solid-phase tack producing: the powder of low viscous PET coated caco3 is placed in 10L rotary drum, heating up and vacuumizing makes object
Expect sufficient crystallising, temperature is 140 DEG C, pressure < 50Pa, time 5h；Heating carries out preliminary thickening and reacts and tie material further
Crystalline substance, temperature are 182 DEG C, time 8h；It further heats up to 210 DEG C, time 5h, discharges.
In gained powder-product, PET viscosity is 1.5dL/g, and the corresponding equal relative molecular weight of number is 6.53 × 104G/mol, carbon
Sour calcium content is 78 weight %.
The preparation of 3 silica of embodiment/polytrimethylene terephthalate composite powder
3.00Kg terephthalic acid (TPA), 2.26Kg propylene glycol, 1.47g isopropyl titanate, heating are put into 10L batch condensation polymerization reactor
Pressurization is esterified, and 200~240 DEG C of temperature, pressure is not higher than 300KPa.Water is distilled out of simultaneously for esterification, the water quilt to theoretical amount
After removing, polycondensation reaction is carried out.After reaching 260 DEG C to polycondensation vessel temperature, carry out polycondensation reaction, system temperature control are vacuumized
System is at 255~260 DEG C, pressure < 50Pa.When polycondensation vessel stirring motor revolution is 25Hz, discharging when electric current reaches 78mA measures spy
Property viscosity number be 0.24dL/g.
Gained PTT oligomer melt after injection mixes, is crushed with the silica of 5000 mesh through crusher and pulverizer
Afterwards (60~100 mesh), it then is further crushed through airslide disintegrating mill, sieves collection cut size in 500~1000 mesh powders.
Powder solid-phase tack producing: the powder of low viscous PTT coated silica is placed in 10L rotary drum, heating up and vacuumizing makes
Material sufficient crystallising, temperature are 120 DEG C, pressure < 50Pa, time 3h；Heating carries out preliminary thickening and reacts and keep material further
Crystallization, temperature are 165 DEG C, time 14h；It further heats up to 215 DEG C, time 6h, discharges.
In gained powder-product, PTT viscosity is 8.5dL/g, and the corresponding equal relative molecular weight of number is 2.93 × 105G/mol, two
Silica content is 76 weight %.
The preparation of 4 titanium dioxide of embodiment/polybutylene terephthalate composite powder
3.00Kg terephthalic acid (TPA), 2.48Kg butanediol, 2.18g isopropyl titanate, heating are put into 10L batch condensation polymerization reactor
Progress decompression esterification, 200~235 DEG C of temperature, 40~60KPa of pressure.Water is distilled out of simultaneously for esterification, and the water to theoretical amount is removed
Later, 2.35g isopropyl titanate is added, carries out polycondensation reaction.After reaching 240 DEG C to polycondensation vessel temperature, vacuumizes and contract
Poly- reaction, system temperature control is at 245 ± 2 DEG C, pressure < 50Pa.When polycondensation vessel stirring motor revolution is 25Hz, electric current reaches
It discharges when 76mA, measuring intrinsic viscosity is 0.19dL/g.
Gained PBT oligomer melt and the titanium dioxide of 200 mesh are after injection mix, after crusher and pulverizer crushing
(60~100 mesh), then further crushed through airslide disintegrating mill, collection cut size is sieved in 150~200 mesh powders.
Powder solid-phase tack producing: the powder of low viscous PBT cladding titanium dioxide is placed in 10L rotary drum, heating up and vacuumizing makes
Material sufficient crystallising, temperature are 140 DEG C, pressure < 50Pa, time 5h；Heating carries out preliminary thickening and reacts and keep material further
Crystallization, temperature are 175 DEG C, time 11h；It further heats up to 210 DEG C, time 17h, discharges.
In gained powder-product, PBT viscosity is 15.5dL/g, and the corresponding equal relative molecular weight of number is 6.78 × 105G/mol,
Content of titanium dioxide is 92 weight %.
The preparation of 5 carbon blacks of embodiment/polybutylene terephthalate composite powder
3.00Kg terephthalic acid (TPA), 2.48Kg butanediol, 2.18g isopropyl titanate, heating are put into 10L batch condensation polymerization reactor
Progress decompression esterification, 200~235 DEG C of temperature, 40~60KPa of pressure.Water is distilled out of simultaneously for esterification, and the water to theoretical amount is removed
Later, 2.35g isopropyl titanate is added, carries out polycondensation reaction.After reaching 240 DEG C to polycondensation vessel temperature, vacuumizes and contract
Poly- reaction, system temperature control is at 245 ± 2 DEG C, pressure < 50Pa.When polycondensation vessel stirring motor revolution is 25Hz, electric current reaches
It discharges when 79mA, measuring intrinsic viscosity is 0.21dL/g.
Gained PBT oligomer melt and the carbon black of 500 mesh are after injection mix, (60 after crusher and pulverizer crushing
~100 mesh), then further crushed through airslide disintegrating mill, collection cut size is sieved in 150~250 mesh powders.
Powder solid-phase tack producing: the powder of low viscous PBT cladding carbon black is placed in 10L rotary drum, heating up and vacuumizing makes material
Sufficient crystallising, temperature are 130 DEG C, pressure < 50Pa, time 6h；Heating carries out preliminary thickening and reacts and crystallize material further,
Temperature is 180 DEG C, time 11h；It further heats up to 210 DEG C, time 5h, discharges.
In gained powder-product, PBT viscosity is 2.5dL/g, and the corresponding equal relative molecular weight of number is 8.35 × 104G/mol, charcoal
Black content is 86 weight %.
Claims (22)
1. a kind of polyester composite containing inorganic matter, composed of the following components:
Polyester shown in logical formula (I):
Wherein, Ar is phenyl, and two ester groups replace on phenyl for contraposition；The integer that m is 2 to 10；N is 50 to 15000；
With
Content is the inorganic matter of 75 weight % or more,
Wherein the composite material is by the powder of the oligomer coated inorganic object of powder solid-phase tack producing, the characteristic of the polyester
Viscosity number is 0.60 to 20.0 dL/g, and the partial size of the composite material is 2000 mesh or less.
2. polyester composite described in claim 1, wherein the content of the inorganic matter is 75 to 98 weight %.
3. polyester composite as claimed in claim 2, wherein the number-average molecular weight of the polyester is 1 x 104To 8 x 106。
4. polyester composite as claimed in claim 2, wherein the number-average molecular weight of the polyester is 2 x 104To 5 x 106。
5. polyester composite as claimed in claim 2, wherein the number-average molecular weight of the polyester is 4 x 104To 4 x 106。
6. polyester composite as claimed in claim 2, wherein the number-average molecular weight of the polyester is 5 x 104To 3.5 x
106。
7. polyester composite as claimed in claim 2, wherein the number-average molecular weight of the polyester is 6 x 104To 3 x 106
g/mol。
8. the described in any item polyester composites of claim 1-7, wherein
The inorganic matter be calcium carbonate, montmorillonite, attapulgite, kaolin, talcum powder, mica, boron nitride, hexagonal boron nitride,
One of stone powder, aluminum oxide, silica, titanium dioxide, carbon black, graphene are a variety of；
The polyester is polyethylene terephthalate, polytrimethylene terephthalate, one in polybutylene terephthalate
Kind is a variety of.
9. polyester composite according to any one of claims 8, wherein the partial size of the composite material is 100 to 2000 mesh.
10. the preparation method of the described in any item polyester composites of claim 1-9, including powder solid-phase tack producing.
11. preparation method described in any one of claim 10, comprising: injection mixing, crushing, screening and powder solid-phase tack producing.
12. preparation method described in claim 11 carries out wherein the powder solid-phase tack producing is heated by the multistage.
13. preparation method described in claim 12, wherein multistage heating includes the following steps:
1) powder of oligomer coated inorganic object is heated to 120~149oC；
2) the resulting material of step 1) is increased into temperature to 150~189oC；
3) the resulting material of step 2 is increased into temperature to 190~220oC, to prepare polyester composite.
14. preparation method described in claim 13, including the following steps:
1) powder of oligomer coated inorganic object is heated to 120~149oC keeps 1 to 8 h；
2) the resulting material of step 1) is increased into temperature to 150~189oC keeps 2~24 h；
3) the resulting material of step 2 is increased into temperature to 190~220oC keeps 2~24 h, to prepare polyester composite.
15. preparation method described in claim 14, wherein the inherent viscosity of the resulting material of step 2 is 0.40~0.55
dL/g。
16. the described in any item preparation methods of claim 11-15 further include carrying out melt polycondensation before injection mixing.
17. preparation method described in claim 16, wherein the melt polycondensation includes the following steps:
1) in the presence of a catalyst, aromatic diacid Ar (COOH)2With glycol monomer HO (CH2)mOH, in catalyst action
Under, polyester prepolyer is obtained by esterification or ester exchange reaction；
2) for prepolymer under the action of polycondensation catalyst, vacuum polycondensation obtains low-viscosity polyester.
18. method described in claim 17, wherein in the step of melt polycondensation:
Step 1) reaction temperature is 150~280oC, reaction time are 1~5 h, and system pressure is 40~500 KPa；
The intrinsic viscosity of low-viscosity polyester obtained in step 2 is 0.40 dL/g hereinafter, condensation temperature is 210~300oC, body
It is pressure for 0~500 Pa, the time is 0.5~10 h.
19. including the printed material of the described in any item polyester composites of claim 1-9.
20. printed material described in claim 19 is 3D printing material.
21. the purposes that the described in any item polyester composites of claim 1-9 are used to prepare printed material.
22. purposes described in claim 21, wherein the printed material is 3D printing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410181466.6A CN103980674B (en) | 2014-04-30 | 2014-04-30 | A kind of polyester powder and preparation method thereof of high inorganic content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410181466.6A CN103980674B (en) | 2014-04-30 | 2014-04-30 | A kind of polyester powder and preparation method thereof of high inorganic content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103980674A CN103980674A (en) | 2014-08-13 |
| CN103980674B true CN103980674B (en) | 2019-03-08 |
Family
ID=51272855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410181466.6A Active CN103980674B (en) | 2014-04-30 | 2014-04-30 | A kind of polyester powder and preparation method thereof of high inorganic content |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103980674B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189116A (en) * | 2016-08-09 | 2016-12-07 | 叶伟然 | A kind of novel graphite alkene flame-retardant PBT and preparation method thereof |
| CN108570222A (en) * | 2018-03-08 | 2018-09-25 | 广东纳路纳米科技有限公司 | White graphite alkene is modified polybutylene terephthalate (PBT) composite material and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554455A (en) * | 2013-10-09 | 2014-02-05 | 杭州福斯特光伏材料股份有限公司 | Copolyester thermoplastic material used for three-dimensional printing, and preparation and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709676A (en) * | 2012-09-29 | 2014-04-09 | 青岛欣展塑胶有限公司 | Functional white master batch for PBT and preparation method thereof |
| CN103110979B (en) * | 2013-02-09 | 2015-06-17 | 复旦大学 | High molecular porous material with surface deposited bone-like hydroxyapatite as well as preparation method and application thereof |
-
2014
- 2014-04-30 CN CN201410181466.6A patent/CN103980674B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554455A (en) * | 2013-10-09 | 2014-02-05 | 杭州福斯特光伏材料股份有限公司 | Copolyester thermoplastic material used for three-dimensional printing, and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103980674A (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102205169B1 (en) | Nucleated crystallization of poly(trimethylene-2,5-furandicarboxylate)(ptf) and articles made therefrom | |
| CN111186112B (en) | Preparation method of novel thermotropic liquid crystal high-performance polyarylate film | |
| US8987343B2 (en) | Branched poly (hydroxy acid) and production process thereof | |
| CN104389045A (en) | Preparation method of thermotropic liquid crystal polyarylester fiber | |
| EP2480589A1 (en) | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof | |
| WO2010100959A1 (en) | Polyester film for solar cell, and process for producing same | |
| WO2012029393A1 (en) | Polylactic acid block copolymer | |
| JP2019513847A (en) | Polyester resin | |
| TW201731908A (en) | Polyester resin, preparation method thereof and resin article formed therefrom | |
| EP2573136A2 (en) | Blend of polylactic acid resin and copolyester resin, and molded product using same | |
| CN103980674B (en) | A kind of polyester powder and preparation method thereof of high inorganic content | |
| CN103980467B (en) | High-viscosity polyester powder for 3D printing and preparation method thereof | |
| CN106435807A (en) | Method for preparing wholly-aromatic polyester fibers based on 4,4'-diaminodiphenyl ether | |
| CN103703050A (en) | Solid phase polymerization method for preparing high molecular weight aliphatic polyester | |
| CN104558557B (en) | High-viscosity polyester-polycarbonate material for 3D printing and preparation method thereof | |
| TW201437251A (en) | Polylactic resin composition, molded product, and method for producing polylactic resin composition | |
| CN105524262A (en) | Preparation methods for poly(polybutylene glycol-adipate-terephthalate) and polylactic-acid block copolymer of poly(polybutylene glycol-adipate-terephthalate) | |
| CN102796071B (en) | The method being manufactured lactide by lactic acid | |
| CN112969740B (en) | Resin composition capable of reducing anisotropy by melting and resin molded article formed from the resin composition | |
| TW200813116A (en) | Modified copolyester, manufactured thermal-shrinkage polyester film thereof, and the manufacturing method of the same | |
| CN109535404B (en) | Preparation method of thermotropic liquid crystal polyarylate | |
| CN102786676B (en) | Polyester elastomer with branching structure and preparation method thereof | |
| WO2007052294A3 (en) | An improved process for the production of slow crystallizing polyester resin | |
| CN1266860A (en) | Transparent article of polyester resin | |
| CN109535402B (en) | Preparation method of polyarylate based on 2- (4-hydroxyphenyl) -5-carboxypyridoimidazole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |