CN117447687A - Low-warpage high-viscosity PETG copolyester and preparation method thereof - Google Patents
Low-warpage high-viscosity PETG copolyester and preparation method thereof Download PDFInfo
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- CN117447687A CN117447687A CN202311767219.XA CN202311767219A CN117447687A CN 117447687 A CN117447687 A CN 117447687A CN 202311767219 A CN202311767219 A CN 202311767219A CN 117447687 A CN117447687 A CN 117447687A
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 33
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 11
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010445 mica Substances 0.000 claims abstract description 7
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229920000180 alkyd Polymers 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 150000003384 small molecules Chemical class 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 claims description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000010146 3D printing Methods 0.000 abstract description 7
- 229920000728 polyester Polymers 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- -1 small molecule diols Chemical class 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5445—Silicon-containing compounds containing nitrogen containing at least one Si-N bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a low-warpage high-viscosity PETG copolyester and a preparation method thereof, and belongs to the technical field of 3D printing materials. The copolyester takes terephthalic acid, ethylene glycol and 1, 4-cyclohexanedimethanol as base materials, small molecular diacid and dihydric alcohol are introduced to copolymer and destroy the regularity of molecular chain segments, the crystallinity of the polymer is reduced, and particularly, a tackifying and anti-warping auxiliary agent is introduced to interact with ultrafine mica powder and nano silicon dioxide to reduce the warping property of the copolyester, wherein the flaky mica powder and the nano silicon dioxide form a geocell structure as a framework, the tackifying and anti-warping auxiliary agent is coupled with the surface of a filler, and meanwhile, polyester crosslinking is participated in, a filling layer with high crosslinking degree is formed between the frameworks, so that the framework and a copolyester matrix form an organic-inorganic integral structure, and the anti-warping effect is improved well.
Description
Technical Field
The invention belongs to the technical field of 3D printing materials, and particularly relates to a low-warpage high-viscosity PETG copolyester and a preparation method thereof.
Background
With the development of science and technology, the aesthetic of things is gradually improved, and the additive manufacturing (3D printing) technology is a manufacturing technology for accurately completing complex shapes by adopting a computer software modeling model and controlling material molding by a numerical control system. The method is widely applied to the fields of military industry, aerospace, medical appliances, automobile manufacturing and the like.
Currently, 3D printing techniques mainly include: fused Deposition Modeling (FDM), light-cured three-dimensional modeling, layered entity manufacturing modeling, electron beam selective melting modeling and the like, wherein the FDM technology has the characteristics of low equipment cost, stable material product size and the like, and becomes the 3D printing technology with the highest marketization and commercialization degree and the fastest growth. The thermoplastic resin is generally used for printing and forming, and mainly comprises materials such as Polycarbonate (PC), polylactic acid (PLA), PETG polyester and the like, wherein the PETG polyester is copolyester, has excellent optical performance and good processability, has excellent properties such as non-toxicity, environmental protection and the like, and is an excellent raw material for 3D printing. However, the problem of buckling deformation exists in the existing PETG polyester material after printing, the precision of a printed product is affected, and the high-definition development of the 3D printing technology is limited.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide low-warpage high-viscosity PETG copolyester and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of low-warpage high-viscosity PETG copolyester comprises the following steps:
step S1: taking terephthalic acid, ethylene glycol and 1, 4-cyclohexanedimethanol as base materials, and adding small-molecule dibasic acid, small-molecule dihydric alcohol, tackifying and anti-warping auxiliary agent, germanium catalyst, stabilizer, antioxidant and filler to mix uniformly to obtain a batch;
further, the molar ratio of the total alkyd in the batch is 1.1-1.5:1.
further, the molar ratio of terephthalic acid, ethylene glycol and 1, 4-cyclohexanedimethanol in the base material is 1:0.8:0.2.
Further, the small molecule diacid is one or two of isophthalic acid and phthalic acid.
Further, the small molecule diols include one or more of diethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, and 2-methyl-1, 3-propanediol.
Further, the dosage of the tackifying and anti-warping auxiliary agent is 6.5-8.5wt% of the base material.
Further, the filler is compounded by superfine mica powder and nano silicon dioxide, and the dosage is 4-6.8wt% of the base material.
Step S2: transferring the batch into a reaction kettle, controlling the liquid temperature to be 220-240 ℃ under the nitrogen atmosphere, controlling the pressure in the kettle to be 0.2-0.25MPa, carrying out esterification reaction for 3.2-4h, adding a titanium catalyst, continuously heating to 275+/-5 ℃, decompressing to below 100Pa, carrying out polycondensation reaction for 1.6-2.2h, and discharging after the reaction is finished, and drawing to obtain the low-warpage high-viscosity PETG copolyester.
The tackifying and anti-warping auxiliary is prepared by the following method:
step A1: uniformly mixing diethanolamine, triethylamine and tetrahydrofuran, introducing dry nitrogen for protection, controlling the temperature in a water bath to be 35-45 ℃, applying 20-28kHz ultrasonic vibration, slowly adding methyl vinyl dichlorosilane, controlling the total adding reaction time to be 1.2-1.6h, and removing low-boiling substances mainly including tetrahydrofuran after the reaction is finished to obtain a hydroxysilazane derivative;
further, the usage ratio of methylvinyldichlorosilane, diethanolamine, triethylamine and tetrahydrofuran was 0.1mol:0.21-0.22mol:15-20mL:100-130mL of methyl vinyl dichlorosilane chloride group and active secondary amine of diethanolamine, the specific reaction route can be expressed as follows:
step A2: uniformly mixing a hydroxy silazane derivative, gamma-mercaptopropyl trimethoxy silane, dimethyl phenyl phosphine and absolute ethyl alcohol, introducing dry nitrogen for protection, heating to 50-60 ℃ with the assistance of 150-200W/m 2 Performing ultraviolet irradiation and mechanical stirring at 180-240rpm, performing constant-temperature irradiation stirring reaction for 2.5-3.3h, and removing ethanol after the reaction is finished to obtain a tackifying and anti-warping auxiliary agent;
further, the ratio of the amounts of the hydroxysilazane derivative, γ -mercaptopropyl trimethoxysilane, dimethylphenylphosphine and absolute ethanol was 0.1mol:0.12 to 0.14mol:40-50mg:200-250mL, wherein the active mercapto group of gamma-mercaptopropyl trimethoxy silane and unsaturated double bond in the hydroxy silazane derivative are subjected to click reaction under initiation, and the specific reaction route can be expressed as follows:
the invention has the beneficial effects that:
the invention discloses a multi-element copolymerization modified PETG polyester material, which is suitable for FDM printing by introducing micromolecular dibasic acid and dihydric alcohol to damage the regularity of molecular chain segments, reducing the crystallinity of a polymer, and being capable of being melted and remolded at a temperature of 250 ℃; the tackifying and anti-warping auxiliary agent is particularly introduced to interact with ultrafine mica powder and nano silicon dioxide to reduce the warping property of the copolyester, the tackifying and anti-warping auxiliary agent is prepared into a hydroxy silazane derivative with a branched hydroxy structure by substitution reaction of methyl vinyl dichlorosilane and diethanolamine, and then gamma-mercaptopropyl trimethoxy silane is added by clicking with unsaturated double bonds in the structure of the hydroxy silazane derivative, so that the structure of grafted methoxy silane is modified; mica powder in the filler is in a sheet structure, forms a geocell structure with nano silicon dioxide, and is used as a framework in a copolyester matrix, and the framework structure has excellent deformation resistance; the methoxy silane structure in the tackifying and anti-warping auxiliary agent is coupled with the surface of the filler in the high-temperature reaction process, and the branched hydroxyl groups of the tackifying and anti-warping auxiliary agent are crosslinked and filled between the frameworks to strengthen the framework structure.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1, a low-warpage high-viscosity PETG copolyester was synthesized, and the specific implementation process was as follows:
1) Preparing the tackifying and anti-warping auxiliary agent
Step A1: taking diethanolamine, triethylamine and tetrahydrofuran, stirring and mixing uniformly, introducing dry nitrogen for protection, controlling the temperature in a water bath to be nitrogen for protection, performing ultrasonic vibration at 20kHz, slowly adding methyl vinyl dichlorosilane within 1h, continuing constant-temperature reaction after complete addition, and controlling the total addition reaction time of the methyl vinyl dichlorosilane to be 1.6h, wherein the dosage ratio of the methyl vinyl dichlorosilane, the diethanolamine, the triethylamine to the tetrahydrofuran is 0.1mol:0.21mol:15mL:100mL, and after the reaction, the low-boiling-point substances mainly containing the solvent tetrahydrofuran are rapidly removed by reduced pressure rotary evaporation, thus obtaining the hydroxy silazane derivative.
Step A2: charging and stirring the hydroxysilazane derivative, gamma-mercaptopropyl trimethoxysilane, dimethylphenylphosphine and absolute ethanol, mixing, introducing dry nitrogen again for protection, heating to 50deg.C, and using UVA lamp at 150W/m 2 Ultraviolet irradiation, mechanical stirring at stirring speed of 180rpm, constant temperature irradiation stirring reaction for 3.3 hr, and during the reaction, hydroxy siliconThe dosage ratio of the nitrogen derivative, the gamma-mercaptopropyl trimethoxysilane, the dimethylphenylphosphine and the absolute ethanol is 0.1mol:0.12mol:40mg:200mL, and removing ethanol by reduced pressure rotary evaporation after the reaction is finished, thus obtaining the tackifying and anti-warping auxiliary agent.
2) Synthetic copolyesters
Step S1: taking terephthalic acid, ethylene glycol and 1, 4-cyclohexanedimethanol as base materials according to the molar ratio of 1:0.8:0.2;
taking isophthalic acid with the dosage of 20wt% and phthalic acid with the dosage of 3wt% as micromolecular dibasic acid;
diethylene glycol and 1, 6-hexanediol are taken according to the mol ratio of 1:1, compounding to be used as micromolecular dihydric alcohol;
taking the tackifying and anti-warping auxiliary agent which is prepared by more than 8.5 weight percent of the base material;
taking germanium catalyst with the base material dosage of 0.3 wt% (germanium dioxide is adopted in the implementation process);
taking a stabilizer (triphenyl phosphate is adopted in the implementation process) accounting for 0.1 weight percent of the base material;
taking an antioxidant accounting for 0.15 weight percent of the base material (the antioxidant 1010 is adopted in the implementation process);
taking filler with the base material dosage of 6.8wt% (in the implementation process, 5000-mesh mica powder and nano-scale silicon dioxide are compounded according to the mass ratio of 3:1);
the raw materials are added into a high-speed mixer, and the mole ratio of the total alkyd is regulated to be 1.1 by using small molecular dihydric alcohol: 1, stirring and mixing uniformly to prepare the batch.
Step S2: transferring the batch into a reaction kettle, adding high-purity nitrogen, heating and controlling the liquid temperature to 240 ℃, controlling the pressure in the kettle to 0.25MPa, carrying out esterification reaction for 3.2 hours, adding 1 wt%of titanium catalyst (tetrabutyl titanate is adopted in the implementation process) of the base material, continuously heating to 275+/-5 ℃, decompressing to below 100Pa, carrying out polycondensation reaction for 2.2 hours, and discharging after the reaction is finished, and drawing to obtain the low-warpage high-viscosity PETG copolyester.
Example 2, a low-warpage high-viscosity PETG copolyester was synthesized, and the specific implementation process was as follows:
1) Preparing the tackifying and anti-warping auxiliary agent
Step A1: taking diethanolamine, triethylamine and tetrahydrofuran, stirring and mixing uniformly, introducing dry nitrogen for protection, controlling the temperature in a water bath to be nitrogen for protection, performing ultrasonic vibration at 28kHz, slowly adding methyl vinyl dichlorosilane within 40min, continuing constant-temperature reaction after complete addition, and controlling the total addition reaction time of the methyl vinyl dichlorosilane to be 1.2h, wherein the dosage ratio of the methyl vinyl dichlorosilane, the diethanolamine, the triethylamine to the tetrahydrofuran is 0.1mol:0.22mol:20mL:130mL, and rapidly removing low-boiling substances mainly comprising solvent tetrahydrofuran by reduced pressure rotary evaporation after the reaction is finished, thus obtaining the hydroxy silazane derivative.
Step A2: charging and stirring the hydroxysilazane derivative, gamma-mercaptopropyl trimethoxysilane, dimethylphenylphosphine and absolute ethanol, mixing, introducing dry nitrogen again for protection, heating to 60 ℃, and using a UVA lamp at 200W/m 2 Ultraviolet irradiation, mechanical stirring at the stirring speed of 240rpm, constant-temperature irradiation stirring reaction for 2.5h, wherein in the reaction, the dosage ratio of the hydroxy silazane derivative, gamma-mercaptopropyl trimethoxy silane, dimethyl phenyl phosphine and absolute ethyl alcohol is 0.1mol:0.14mol:50mg:250mL, and removing ethanol by reduced pressure rotary evaporation after the reaction is finished, thus obtaining the tackifying and anti-warping auxiliary agent.
2) Synthetic copolyesters
Step S1: taking terephthalic acid, ethylene glycol and 1, 4-cyclohexanedimethanol as base materials according to the molar ratio of 1:0.8:0.2;
taking 15wt% of isophthalic acid and 5wt% of phthalic acid as small molecular dibasic acid;
diethylene glycol and 1, 3-propanediol are taken according to the mol ratio of 1:1, compounding to be used as micromolecular dihydric alcohol;
taking the tackifying and anti-warping auxiliary agent which is prepared by more than 6.5 weight percent of the base material;
taking germanium catalyst with the base material dosage of 0.25 wt%;
taking a stabilizer accounting for 0.1 weight percent of the base material;
taking an antioxidant accounting for 0.15 weight percent of the base material;
taking filler accounting for 4 weight percent of the base material;
the raw materials are added into a high-speed mixer, and the mole ratio of the total alkyd is regulated to be 1.5 by using small molecular dihydric alcohol: 1, stirring and mixing uniformly to prepare the batch.
Step S2: transferring the batch into a reaction kettle, adding high-purity nitrogen, heating and controlling the liquid temperature to 220 ℃, controlling the pressure in the kettle to be 0.2MPa, esterifying for 4 hours, adding 1 wt%of titanium catalyst of base material, continuously heating to 275+/-5 ℃, decompressing to below 100Pa, polycondensing for 1.6 hours, discharging and dragging to obtain the low-warpage high-viscosity PETG copolyester after the reaction is finished.
Example 3, a low-warpage high-viscosity PETG copolyester was synthesized, and the specific implementation process was as follows:
1) Preparing the tackifying and anti-warping auxiliary agent
Step A1: taking diethanolamine, triethylamine and tetrahydrofuran, stirring and mixing uniformly, introducing dry nitrogen for protection, controlling the temperature in a water bath to be nitrogen for protection, performing ultrasonic vibration at 25kHz, slowly adding methyl vinyl dichlorosilane within 1h, continuing constant-temperature reaction after complete addition, and controlling the total addition reaction time of the methyl vinyl dichlorosilane to be 1.4h, wherein the dosage ratio of the methyl vinyl dichlorosilane, the diethanolamine, the triethylamine to the tetrahydrofuran is 0.1mol:0.21mol:18mL:120mL, the reaction is finished, the low-boiling-point substances mainly containing solvent tetrahydrofuran are rapidly removed by reduced pressure rotary evaporation, and the hydroxy silazane derivative is prepared.
Step A2: charging and stirring the hydroxysilazane derivative, gamma-mercaptopropyl trimethoxysilane, dimethylphenylphosphine and absolute ethanol, mixing, introducing dry nitrogen again for protection, heating to 60 ℃, and using a UVA lamp at 180W/m 2 And (3) carrying out ultraviolet irradiation, simultaneously controlling the stirring speed to be 240rpm, carrying out mechanical stirring, and controlling constant-temperature irradiation stirring reaction for 3 hours, wherein in the reaction, the dosage ratio of the hydroxy silazane derivative, gamma-mercaptopropyl trimethoxy silane, dimethyl phenyl phosphine and absolute ethyl alcohol is 0.1mol:0.13mol:40mg:220mL, and removing ethanol by reduced pressure rotary evaporation after the reaction is finished, thus obtaining the tackifying and anti-warping auxiliary agent.
2) Synthetic copolyesters
Step S1: taking terephthalic acid, ethylene glycol and 1, 4-cyclohexanedimethanol as base materials according to the molar ratio of 1:0.8:0.2;
taking 15wt% of isophthalic acid and 4wt% of phthalic acid as small molecular dibasic acid;
taking 1, 4-butanediol and 2-methyl-1, 3-propanediol according to a molar ratio of 1:1, compounding to be used as micromolecular dihydric alcohol;
taking the tackifying and anti-warping auxiliary agent which is prepared by more than 7.2 weight percent of the base material;
taking germanium catalyst with the base material dosage of 0.28 wt%;
taking a stabilizer accounting for 0.1 weight percent of the base material;
taking an antioxidant accounting for 0.15 weight percent of the base material;
taking filler with the amount of 5.5wt% of the base material;
the raw materials are added into a high-speed mixer, and the mole ratio of the total alkyd is regulated to be 1.3 by using small molecular dihydric alcohol: 1, stirring and mixing uniformly to prepare the batch.
Step S2: transferring the batch into a reaction kettle, adding high-purity nitrogen, heating and controlling the liquid temperature to be 230 ℃, controlling the pressure in the kettle to be 0.2MPa, carrying out esterification reaction for 3.5 hours, adding 1 wt%titanium catalyst of the base material, continuously heating to 275+/-5 ℃, decompressing to below 100Pa, carrying out polycondensation reaction for 1.8 hours, and discharging and dragging to obtain a wire material after the reaction is finished, thus obtaining the low-warpage high-viscosity PETG copolyester.
Comparative example 1
This ratio is shown in example 3, and the rest of the procedure is identical to example 3, except that no adhesion promoting and anti-warping additive is added to the batch.
Comparative example 2
This comparative example is referred to example 3, using a single nanosilica as filler in an amount of 4.2% by weight of the base material, and the remainder of the procedure is identical to example 3.
Comparative example 3
This comparative example is a commercial PETG wire, supplied by Shenzhen Guanghua West company, inc.
Phenol and tetrachloroethane are mixed according to the mass ratio of 1:1, mixing and preparing a solvent, respectively adding the wires prepared in the examples and the comparative examples, preparing a solution with the concentration of 1g/100mL, and measuring the intrinsic viscosity of the solution in a constant-temperature water bath at 25 ℃ by adopting a Ubbelohde viscometer;
loading the prepared wire into a 3D printer, taking stainless steel as a bottom plate, printing at 240 ℃, heating a hot bed at 50 ℃, printing at 80mm/s, printing an adhesive layer on the surface of the bottom plate, and performing a peeling test according to GB/T2790-1995 standard;
loading the prepared wire into a 3D printer, printing a cube model with the specification of 10 multiplied by 10cm according to the parameters, cooling, and detecting the maximum gap between the model and the bottom plate by adopting a three-coordinate system measuring instrument to be recorded as the warpage; the specific test data are shown in table 1:
TABLE 1
As shown in the data of Table 1, with the addition of the tackifying and anti-warping auxiliary agent, the crosslinking degree of the copolymer material is increased, the intrinsic viscosity is higher, the peel strength reaches 30.4-38.2N/25mm in the test at 0.75-0.81dL/g, the peel strength is higher, the printed product is not easy to fall off and does not influence the workpiece taking, and the warping amount is only 0.13-0.21mm, which is obviously better than that of the comparative example.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (10)
1. The preparation method of the low-warpage high-viscosity PETG copolyester is characterized by comprising the following steps:
step S1: taking terephthalic acid, ethylene glycol and 1, 4-cyclohexanedimethanol as base materials, and adding small-molecule dibasic acid, small-molecule dihydric alcohol, tackifying and anti-warping auxiliary agent, germanium catalyst, stabilizer, antioxidant and filler to mix uniformly to obtain a batch;
step S2: transferring the batch into a reaction kettle, controlling the liquid temperature to be 220-240 ℃ under the nitrogen atmosphere, controlling the pressure in the kettle to be 0.2-0.25MPa, carrying out esterification reaction for 3.2-4h, adding a titanium catalyst, continuously heating to 275+/-5 ℃, decompressing to below 100Pa, carrying out polycondensation reaction for 1.6-2.2h, and discharging after the reaction is finished, and drawing to obtain the low-warpage high-viscosity PETG copolyester.
2. The method for preparing the low-warpage high-viscosity PETG copolyester according to claim 1, wherein the tackifying and anti-warpage auxiliary agent is prepared by the following steps:
step A1: uniformly mixing diethanolamine, triethylamine and tetrahydrofuran, introducing dry nitrogen for protection, controlling the temperature in a water bath to be 35-45 ℃, applying 20-28kHz ultrasonic vibration, slowly adding methyl vinyl dichlorosilane, controlling the total adding reaction time to be 1.2-1.6h, and removing tetrahydrofuran after the reaction is finished to obtain a hydroxysilazane derivative;
step A2: uniformly mixing a hydroxy silazane derivative, gamma-mercaptopropyl trimethoxy silane, dimethyl phenyl phosphine and absolute ethyl alcohol, introducing dry nitrogen for protection, heating to 50-60 ℃ with the assistance of 150-200W/m 2 Ultraviolet irradiation, constant temperature irradiation stirring reaction for 2.5-3.3h, and removing ethanol after the reaction is finished, thus obtaining the tackifying and anti-warping auxiliary agent.
3. The method for preparing the low-warpage high-viscosity PETG copolyester according to claim 2, wherein the dosage ratio of methylvinyldichlorosilane, diethanolamine, triethylamine and tetrahydrofuran is 0.1mol:0.21-0.22mol:15-20mL:100-130mL.
4. The method for preparing the low-warpage high-viscosity PETG copolyester according to claim 3, wherein the dosage ratio of the hydroxysilazane derivative, the gamma-mercaptopropyl trimethoxysilane, the dimethylphenylphosphine and the absolute ethyl alcohol is 0.1mol:0.12 to 0.14mol:40-50mg:200-250mL.
5. The method for preparing the low-warpage high-viscosity PETG copolyester according to claim 4, wherein the amount of the tackifying and anti-warpage auxiliary agent is 6.5-8.5wt% of the base material, and the molar ratio of the total alkyd in the batch is 1.1-1.5:1.
6. the method for preparing the low-warpage high-viscosity PETG copolyester according to claim 5, wherein the molar ratio of the terephthalic acid to the ethylene glycol to the 1, 4-cyclohexanedimethanol in the base material is 1:0.8:0.2.
7. The method for preparing the low-warpage high-viscosity PETG copolyester according to claim 6, wherein the small molecular dibasic acid is one or both of isophthalic acid and phthalic acid.
8. The method for preparing the low-warpage high-viscosity PETG copolyester according to claim 6, wherein the small molecular dihydric alcohol comprises one or more of diethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol and 2-methyl-1, 3-propanediol.
9. The preparation method of the low-warpage high-viscosity PETG copolyester of claim 6, wherein the filler is compounded by ultrafine mica powder and nano silicon dioxide, and the dosage is 4-6.8wt% of the base material.
10. A low-warpage high-viscosity PETG copolyester prepared by the preparation method of any one of claims 1 to 9.
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