CN117586487B - High-temperature weather-resistant PCTG material and preparation method thereof - Google Patents
High-temperature weather-resistant PCTG material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000005886 esterification reaction Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 16
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 claims abstract description 13
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 13
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 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 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 45
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229960002479 isosorbide Drugs 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C08G63/02—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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2251—Oxides; Hydroxides of metals of chromium
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2289—Oxides; Hydroxides of metals of cobalt
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of PCTG materials, and particularly relates to a high-temperature weather-resistant PCTG material and a preparation method thereof. The method comprises the following steps: (1) Adding PTA, mixed alcohol and a first-stage catalyst into a reaction kettle, and heating to perform esterification reaction to obtain PCTG esterified substances; (2) Continuously carrying out normal-pressure esterification reaction on the obtained PCTG esterified substance, and then adding a coupling agent, a reinforcing agent, nano-scale germanium oxide powder, nano-scale chromium oxide powder and nano-scale cobalt oxide powder for secondary esterification reaction; (3) Continuously adding a second-stage catalyst and a stabilizer to perform a pre-polymerization reaction; (4) After the pre-polycondensation reaches the reaction end point, heating to perform the final polycondensation reaction, thus obtaining the high-temperature weather-proof PCTG material. The nano-scale temperature-resistant metal element is added in the preparation process, so that the PCTG material has excellent temperature resistance and weather resistance under the condition of not reducing the performance of the PCTG material, and has longer service life in severe environments such as outdoors.
Description
Technical Field
The invention belongs to the technical field of PCTG materials, and particularly relates to a high-temperature weather-resistant PCTG material and a preparation method thereof.
Background
PCTG is a thermoplastic polyester plastic having excellent transparency, chemical resistance, impact resistance and processability, and thus is widely used in the fields of construction, medical treatment and industry, gradually replacing conventional materials such as PVC and PC. The PCTG is in the common forms of plates, pipes, bars and films, has excellent durability and impact resistance, and is suitable for high-strength environments such as building decorative plates, including wall surfaces, ceilings, partitions and the like. The PCTG plate with high transparency can be used for manufacturing roofs and skylights, and indoor lighting is increased. In addition, PCTG has high fire-proof grade which can reach B1 grade, and is widely applied to commercial and residential buildings. It also has excellent workability, is customizable, and meets different building requirements. As a recyclable material, PCTG reduces waste of environment and resources, and can be safely incinerated without generating harmful substances. In the construction use, PCTG can not release harmful substance or produce toxic gas because of being heated, and is very safe.
With the improvement of substances and living standards of people, the requirements of people on environment, health and sanitation are higher and higher, and as PCTG is widely applied in daily production and life, the PCTG has higher and higher requirements on the performance of the PCTG, and higher expectations are also raised on the temperature resistance of the PCTG. However, PCTG itself does not have temperature resistance, and since downstream products are applied to various fields and have high expectations for its temperature resistance, development of PCTG having high temperature weather resistance has important significance and value.
In the prior art, most of the temperature resistant materials are prepared by carrying out screw melt blending extrusion granulation on the temperature resistant agent and the materials, and the temperature resistant agent is modified in some processes, but whether the temperature resistant agent is modified or not, PCTG obtained by melt blending still has the defect of uneven mixing, so that the temperature resistant effect is poor, and meanwhile, the process can be realized only by secondary processing, so that the production cost is increased.
Chinese patent CN109762147a discloses a polyethylene terephthalate composition and its preparation method, which is prepared from terephthalic acid or its derivative, ethylene glycol, and isosorbide through esterification and polycondensation, and one or more of silicon dioxide, aluminum oxide, magnesium oxide, and zirconium oxide are added during synthesis. Compared with similar modified polyester, the polyester composition prepared by the invention has the characteristics of excellent temperature resistance, excellent processing flow property, high production efficiency and stable product quality, and can be used as packaging materials, plates, cosmetics and the like. However, the temperature resistance is up to 96 ℃, and the product is not suitable for the field of high temperature resistant materials, especially for weather-proof food-grade edible tableware which is resistant to boiling (100 ℃ in normal pressure boiling water), and needs repeated boiling water boiling.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-temperature weather-resistant PCTG material, which is endowed with excellent temperature-resistant and weather-resistant properties under the condition that the performance of the PCTG material is not reduced by adding nanoscale temperature-resistant metal elements in the preparation process;
the invention further aims to provide a preparation method of the high-temperature weather-resistant PCTG material, which is simple, scientific and reasonable in process and suitable for industrial production.
The technical scheme adopted by the invention is as follows:
the preparation method of the high-temperature weather-resistant PCTG material comprises the following steps:
(1) Esterification reaction: adding PTA, mixed alcohol and a first-stage catalyst into a reaction kettle, heating to perform esterification reaction, wherein the temperature is 210-235 ℃, the pressure is 150-300 kPa, and obtaining PCTG esterified substances when the esterification conversion rate is more than or equal to 90%;
(2) Secondary esterification: continuously carrying out normal-pressure esterification reaction on the obtained PCTG (polyethylene terephthalate glycol) esterified substance for 30-60 min, then adding a coupling agent, a reinforcing agent, nano germanium oxide powder, nano chromium oxide powder and nano cobalt oxide powder for secondary esterification reaction, wherein the temperature is 235-250 ℃, the pressure is 60-80 kPa, and the acid value is detected to be less than or equal to 20mg/g, thus obtaining a reaction end point;
(3) Pre-polycondensation: continuously adding a second-stage catalyst and a stabilizer for pre-polymerization, wherein the temperature is 250-265 ℃, the vacuum degree is 1-3 kPa, and the detection of the intrinsic viscosity is 0.35-0.65 dL/g, namely the reaction end point;
(4) And (3) final polycondensation: after the pre-polycondensation reaches the reaction end point, heating to perform the final polycondensation reaction, wherein the temperature is 265-275 ℃, the vacuum degree is less than or equal to 200Pa, cooling and granulating to obtain the high-temperature weather-resistant PCTG material.
The mixed alcohol is a mixture of Ethylene Glycol (EG) and 1, 4-Cyclohexanedimethanol (CHDM), and the mass ratio of the mixed alcohol to the 1 is (0.55-0.95); the mass ratio of PTA to the mixed alcohol is 1 (0.84-0.94).
The catalyst is a mixture of tetrabutyl titanate, antimony trioxide and stannous octoate, and the mass ratio of the tetrabutyl titanate to the antimony trioxide to the stannous octoate is 4:3:3; the catalyst dosage is 0.015-0.025 wt.% of the total mass of PTA and mixed alcohol.
The dosage of the first-stage catalyst is 0.005-0.01 wt.% of the total mass of PTA and mixed alcohol.
The coupling agent is silane coupling agent, preferably one of KH-560, KH-561 or KH-781, which is purchased from JieXtensil chemical Co., hangzhou, and the dosage of the coupling agent is 0.005-0.015 wt.% of the total mass of PTA and mixed alcohol.
The reinforcing agent is glycerol, and the consumption of the reinforcing agent is 0.02-0.04 wt.% of the total mass of PTA and mixed alcohol.
The dosage of the nano-scale germanium oxide powder is 0.004-0.006wt.% of the total mass of PTA and mixed alcohol;
the dosage of the nano-scale chromium oxide powder is 0.004-0.006wt.% of the total mass of PTA and mixed alcohol;
the dosage of the nano cobalt oxide powder is 0.008-0.010wt% of the total mass of PTA and mixed alcohol.
The stabilizer is triphenyl phosphate, which is purchased from Zhejiang Wansheng Co., ltd, and the amount of the stabilizer is 0.008-0.01 wt.% of the total mass of PTA and the mixed alcohol.
The high-temperature weather-resistant PCTG material is prepared by the preparation method of the high-temperature weather-resistant PCTG material.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the high-temperature weather-resistant PCTG material, the nano germanium oxide powder, the nano chromium oxide powder and the nano cobalt oxide powder are introduced into the formula components, so that the obtained material has excellent temperature resistance under the condition that the original performance is not reduced, can resist a temperature range of-50-120 ℃, meets the use requirement in a high-temperature environment, and has longer service life in outdoor severe environments and the like; meanwhile, the added temperature-resistant metal elements are uniformly distributed in the material, so that the material is ensured to have lasting and excellent temperature resistance; in addition, the structural stability and the reaction efficiency of the material are improved through the 1, 4-cyclohexanedimethanol, and the appearance transparency is improved;
(2) The preparation method of the high-temperature weather-resistant PCTG material is scientific, reasonable, simple and feasible, does not need secondary processing, can reduce the production cost and improves the production efficiency.
Detailed Description
The invention is further illustrated below with reference to examples, which are not intended to limit the practice of the invention.
The raw materials used in examples and comparative examples are conventional commercial raw materials unless otherwise specified, and the process methods used in examples and comparative examples are conventional in the art unless otherwise specified.
Wherein the catalyst is a mixture of tetrabutyl titanate, antimonous oxide and stannous octoate, and the mass ratio of the tetrabutyl titanate, the antimonous oxide and the stannous octoate is 4:3:3
Example 1
The preparation method of the high-temperature weather-resistant PCTG material comprises the following steps:
(1) Esterification reaction: PTA, CHDM, EG with the mass ratio of 2.3:1:0.95 and a first-stage catalyst are added into a reaction kettle, the dosage of the first-stage catalyst is 0.01wt.% of the total mass of PTA and mixed alcohol, the temperature is raised to carry out esterification reaction, the temperature is 210 ℃, the pressure is 300kPa, and when the esterification conversion rate is 91%, PCTG esterified substances are obtained;
(2) Secondary esterification: continuously carrying out normal-pressure esterification reaction on the obtained PCTG esterified product for 60min, then adding KH-560, glycerol, nano-grade germanium oxide powder, nano-grade chromium oxide powder and nano-grade cobalt oxide powder, carrying out secondary esterification reaction at the temperature of 235 ℃ and the pressure of 60kPa, and detecting the acid value of the PCTG esterified product to be 20mg/g, wherein the acid value is the reaction end point, the dosage of KH-560 is 0.015wt.% of the total mass of PTA and mixed alcohol, the dosage of glycerol is 0.04wt.% of the total mass of PTA and mixed alcohol, the dosage of nano-grade germanium oxide powder is 0.006wt.% of the total mass of PTA and mixed alcohol, and the dosage of nano-grade cobalt oxide powder is 0.012wt.% of the total mass of PTA and mixed alcohol;
(3) Pre-polycondensation: continuously adding a second-stage catalyst, namely triphenyl phosphate, performing a pre-polycondensation reaction, wherein the temperature is 250 ℃, the vacuum degree is 3kPa, and detecting that the intrinsic viscosity is 0.35dL/g, namely the reaction end point, wherein the dosage of the second-stage catalyst is 0.015wt.% of the total mass of PTA and mixed alcohol, and the dosage of the triphenyl phosphate is 0.01wt.% of the total mass of PTA and mixed alcohol;
(4) And (3) final polycondensation: after the pre-polycondensation reaches the end of the reaction, heating to perform the final polycondensation reaction at 265 ℃ and 180Pa of vacuum degree, and cooling and granulating to obtain the high-temperature weather-resistant PCTG material.
Example 2
The preparation method of the high-temperature weather-resistant PCTG material comprises the following steps:
(1) Esterification reaction: PTA, CHDM, EG with the mass ratio of 1.92:1:0.72 and a first-stage catalyst are added into a reaction kettle, the dosage of the first-stage catalyst is 0.0075wt.% of the total mass of PTA and mixed alcohol, the temperature is increased to carry out esterification reaction, the temperature is 227 ℃, the pressure is 200kPa, and when the esterification conversion rate is 90%, PCTG esterified substances are obtained;
(2) Secondary esterification: continuously carrying out normal-pressure esterification reaction on the obtained PCTG esterified substance for 45min, then adding a coupling agent KH-561, glycerol, nano-grade germanium oxide powder, nano-grade chromium oxide powder and nano-grade cobalt oxide powder, carrying out secondary esterification reaction at the temperature of 240 ℃ and the pressure of 70kPa, and detecting the acid value of the PCTG esterified substance to be 20mg/g, namely the reaction end point, wherein the dosage of KH-561 is 0.01wt.% of the total mass of PTA and mixed alcohol, the dosage of glycerol is 0.03wt.% of the total mass of PTA and mixed alcohol, the dosage of nano-grade germanium oxide powder is 0.005wt.% of the total mass of PTA and mixed alcohol, and the dosage of nano-grade cobalt oxide powder is 0.005wt.% of the total mass of PTA and mixed alcohol;
(3) Pre-polycondensation: continuously adding a second-stage catalyst, namely triphenyl phosphate serving as a stabilizer, performing pre-polycondensation reaction at 257 ℃, wherein the vacuum degree is 2kPa, and detecting that the intrinsic viscosity is 0.5dL/g, namely the reaction end point, wherein the dosage of the second-stage catalyst is 0.0125wt.% of the total mass of PTA and mixed alcohol, and the dosage of triphenyl phosphate is 0.009wt.% of the total mass of PTA and mixed alcohol;
(4) And (3) final polycondensation: after the pre-polycondensation reaches the reaction end point, heating to perform final polycondensation reaction at 270 ℃ and 190Pa, cooling and granulating to obtain the high-temperature weather-resistant PCTG material.
Example 3
The preparation method of the high-temperature weather-resistant PCTG material comprises the following steps:
(1) Esterification reaction: PTA, CHDM, EG with the mass ratio of 1.65:1:0.55 and a first-stage catalyst are added into a reaction kettle, the dosage of the first-stage catalyst is 0.005wt.% of the total mass of PTA and mixed alcohol, the temperature is increased to carry out esterification reaction, the temperature is 235 ℃, the pressure is 150kPa, and the PCTG esterified product is obtained when the esterification conversion is 92%;
(2) Secondary esterification: continuously carrying out normal-pressure esterification reaction on the obtained PCTG esterified substance for 30min, then adding a coupling agent KH-781, glycerol, nanoscale germanium oxide powder, nanoscale chromium oxide powder and nanoscale cobalt oxide powder, carrying out secondary esterification reaction at the temperature of 250 ℃ under the pressure of 80kPa, and detecting the acid value of the PCTG esterified substance to be 19mg/g, wherein the acid value is the reaction end point, the dosage of KH-781 is 0.005wt.% of the total mass of PTA and mixed alcohol, the dosage of glycerol is 0.02wt.% of the total mass of PTA and mixed alcohol, the dosage of nanoscale germanium oxide powder is 0.004wt.% of the total mass of PTA and mixed alcohol, and the dosage of nanoscale cobalt oxide powder is 0.008wt.% of the total mass of PTA and mixed alcohol;
(3) Pre-polycondensation: continuously adding a second-stage catalyst, namely triphenyl phosphate, performing a pre-polycondensation reaction, wherein the temperature is 265 ℃, the vacuum degree is 1kPa, and detecting that the intrinsic viscosity is 0.65dL/g, namely the reaction end point, wherein the dosage of the second-stage catalyst is 0.01wt.% of the total mass of PTA and mixed alcohol, and the dosage of the triphenyl phosphate is 0.008wt.% of the total mass of PTA and mixed alcohol;
(4) And (3) final polycondensation: after the pre-polycondensation reaches the reaction end point, heating to perform final polycondensation reaction at 275 ℃ and 160Pa of vacuum degree, and cooling and granulating to obtain the high-temperature weather-resistant PCTG material.
Comparative example 1
The difference from example 3 is that the same amount of EG is used instead of CHDM, CHDM is not added to the formulation components, and example 3 is otherwise used.
Comparative example 2
The difference from example 3 is that the formulation components are not added with the nano-sized germanium oxide powder, the nano-sized chromium oxide powder and the nano-sized cobalt oxide powder, which are the same as in example 3.
Comparative example 3
The difference from example 3 is that equal amounts of isosorbide are used instead of CHDM, otherwise the same as in example 3.
Vicat softening temperatures (DEG C) of PCTG materials prepared in examples 1 to 3 and comparative examples 1 to 3 were tested, and the test method was referred to GB/T1633-2000.
The test results are shown in table 1:
TABLE 1 Performance test results
From table 1, it can be seen that the vicat softening temperature of the PCTG material prepared in the example is significantly better than that of the comparative example, which shows that the invention can significantly improve the temperature and weather resistance of the PCTG material by introducing CHDM and temperature-resistant metal elements into the formulation components.
Claims (7)
1. The preparation method of the high-temperature weather-resistant PCTG material is characterized by comprising the following steps:
(1) Esterification reaction: adding PTA, mixed alcohol and a first-stage catalyst into a reaction kettle, heating to perform esterification reaction, and obtaining PCTG esterified substances when the esterification conversion rate is more than or equal to 90%;
(2) Secondary esterification: continuously carrying out normal-pressure esterification reaction on the obtained PCTG esterified substance, then adding a coupling agent, a reinforcing agent, nano germanium oxide powder, nano chromium oxide powder and nano cobalt oxide powder, carrying out secondary esterification reaction, and detecting that the acid value is less than or equal to 20mg/g, namely the reaction end point;
(3) Pre-polycondensation: continuously adding a second-stage catalyst and a stabilizer for pre-polymerization, and detecting that the intrinsic viscosity of the catalyst is 0.35-0.65 dL/g, namely the reaction end point;
(4) And (3) final polycondensation: after the pre-polycondensation reaches the reaction end point, heating to perform a final polycondensation reaction to obtain the high-temperature weather-resistant PCTG material;
the mixed alcohol is a mixture of glycol and 1, 4-cyclohexanedimethanol, and the mass ratio of the mixed alcohol to the 1 is (0.55-0.95);
the catalyst is a mixture of tetrabutyl titanate, antimony trioxide and stannous octoate, and the mass ratio of the tetrabutyl titanate to the antimony trioxide to the stannous octoate is 4:3:3; the catalyst dosage is 0.015-0.025 wt.% of the total mass of PTA and mixed alcohol;
the reinforcing agent is glycerol, and the consumption of the reinforcing agent is 0.02-0.04 wt.% of the total mass of PTA and mixed alcohol;
the dosage of the nano-scale germanium oxide powder is 0.004-0.006wt.% of the total mass of PTA and mixed alcohol;
the dosage of the nano-scale chromium oxide powder is 0.004-0.006wt.% of the total mass of PTA and mixed alcohol;
the dosage of the nano cobalt oxide powder is 0.008-0.010wt% of the total mass of PTA and mixed alcohol.
2. The method for preparing the high-temperature weather-resistant PCTG material according to claim 1, wherein the mass ratio of PTA to the mixed alcohol is 1 (0.84-0.94).
3. The method for preparing the high-temperature weather-resistant PCTG material according to claim 1, wherein the amount of the catalyst used in the first stage is 0.005-0.01 wt.% of the total mass of PTA and the mixed alcohol.
4. The method for preparing the high-temperature weather-resistant PCTG material according to claim 1, wherein the coupling agent is a silane coupling agent, and the amount of the coupling agent is 0.005-0.015 wt.% of the total mass of PTA and the mixed alcohol.
5. The method for preparing the high-temperature weather-resistant PCTG material according to claim 1, wherein the stabilizer is triphenyl phosphate, and the amount of the stabilizer is 0.008-0.01 wt.% of the total mass of PTA and the mixed alcohol.
6. The method for preparing a high-temperature weather-resistant PCTG material according to claim 1, wherein in the step (1), the esterification reaction temperature is 210-235 ℃; in the step (2), the normal pressure esterification reaction time is 30-60 min, and the secondary esterification reaction temperature is 235-250 ℃; in the step (3), the pre-polycondensation reaction temperature is 250-265 ℃ and the vacuum degree is 1-3 kPa; in the step (4), the final polycondensation reaction temperature is 265-275 ℃, and the vacuum degree is less than or equal to 200Pa.
7. The high-temperature weather-resistant PCTG material is characterized by being prepared by the preparation method of the high-temperature weather-resistant PCTG material disclosed in any one of claims 1-6.
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