CN114539726B - High-toughness polyester resin material and preparation method thereof - Google Patents
High-toughness polyester resin material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 33
- 239000004645 polyester resin Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 37
- 229920001971 elastomer Polymers 0.000 claims abstract description 26
- 239000000806 elastomer Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 22
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 18
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 9
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 14
- 239000000178 monomer Substances 0.000 abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 229920003225 polyurethane elastomer Polymers 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000229 biodegradable polyester Polymers 0.000 description 3
- 239000004622 biodegradable polyester Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- 241000234295 Musa Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- 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 discloses a high-toughness polyester resin material and a preparation method thereof, wherein the raw materials of the high-toughness polyester resin material at least comprise the following components in parts by weight: 30-50 parts of dihydric alcohol, 70-90 parts of dibasic acid, 10-20 parts of carboxylic acid monomer, 8-10 parts of auxiliary agent, 10-20 parts of elastic particles and 5-10 parts of catalyst, wherein the elastic particles are at least one of polymer elastomer particles. The high-toughness polyester resin material prepared by the method has good rigidity, mechanical property and chemical resistance, effectively enhances the toughness of the polyester elastomer, is suitable for popularization in the field of polyester resin, and has wide development prospect.
Description
Technical Field
The invention relates to the field of C08G, in particular to a high-toughness polyester resin material and a preparation method thereof.
Background
With the advancement of society and the development of economy, and the increasing environmental pressure, attention is increasingly paid to degradable green materials, and particularly in recent years, research and development and utilization of degradable polymer materials have attracted a wide range of attention in the field of materials.
Particularly, in the field of degradable polyester resin materials, research has been focused on polymer materials in recent years. The prior art (CN 201480071441.9) provides a preparation method of biodegradable polyester resin, which mainly prepares a polyester resin material capable of being effectively biodegradable through dicarboxylic acid, diol, catalyst and deactivator capable of reducing the activity of the catalyst, but lacks the addition of related modified or rigid monomers, can not effectively improve the toughness, mechanical properties and other properties of the degradable polyester resin material, and greatly reduces the application field and environment of the polyester material.
Therefore, it is a very interesting task to develop a biodegradable polyester resin material having excellent rigidity, toughness and mechanical strength.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides a high-toughness polyester resin material, which comprises at least the following raw materials in parts by mass: 30-50 parts of dihydric alcohol, 70-90 parts of dibasic acid, 10-20 parts of carboxylic acid monomer, 8-10 parts of auxiliary agent, 10-20 parts of elastic particles and 5-10 parts of catalyst;
the elastic particles are at least one of polymer elastomer particles.
As a preferable scheme, the dihydric alcohol is at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol and 1, 4-butanediol.
As a preferred embodiment, the diol is 1, 4-butanediol.
As a preferable scheme, the dibasic acid is at least one of phthalic acid, dodecanedioic acid, malonic acid, succinic acid, glutaric acid and suberic acid.
As a preferred embodiment, the dibasic acid is phthalic acid.
As a preferable scheme, the mass ratio of the dihydric alcohol to the dibasic acid is 7-8: 15 to 16.
As a preferable scheme, the mass ratio of the dihydric alcohol to the dibasic acid is 7:15.
as a preferred embodiment, the carboxylic acid monomer is at least one of isohexide dicarboxylic acid monomers.
As a preferred embodiment, the carboxylic acid monomer is isosorbide-2, 5-dicarboxylic acid.
As a preferable scheme, the mass ratio of the carboxylic acid monomer to the dihydric alcohol is 2-3: 7-8.
As a preferable scheme, the mass ratio of the carboxylic acid monomer to the dihydric alcohol is 3:7.
in the application, the isosorbide-2, 5-dicarboxylic acid is added as the modified monomer of the polyester resin material, so that the rigidity, mechanical strength and biodegradability of the polyester resin material are effectively improved. The applicant speculates that: when isosorbide-2, 5-dicarboxylic acid is adopted as a carboxylic acid monomer and the mass ratio of the isosorbide-2, 5-dicarboxylic acid to the dihydric alcohol is 3:7, the isosorbide-2, 5-dicarboxylic acid has better carboxyl group reactivity, and can be effectively connected with the annular framework structure of the polyester material, so that the phenomenon of shorter molecular chain connection caused by low reactivity of secondary hydroxyl is avoided, and the overall length and the overall molecular weight of the molecular chain of the polyester material are finally and effectively improved, and the biodegradability of the polyester resin material is improved.
As a preferable scheme, the auxiliary agent is at least one of p-phenylenediamine, p-diphenol, thiobisphenol, triphenol and diphenylamine.
As a preferred embodiment, the auxiliary agents are p-phenylenediamine and p-diphenol.
As a preferable scheme, the mass ratio of the p-phenylenediamine to the p-diphenol is 1-2: 1 to 2.
As a preferred scheme, the mass ratio of the p-phenylenediamine to the p-diphenol is 1.5:1.
in the application, through the synergistic addition of p-phenylenediamine and p-diphenol, the long-term yellowing resistance stability, the service life and the solvent resistance of the polyester material are effectively improved. The applicant speculates that: the addition of the p-phenylenediamine and the p-diphenol can effectively reduce the electron loss phenomenon of the atoms in the resin in a synergic manner, and has better long-term effectiveness, mainly because the addition of the p-diphenol can effectively promote the chemical regeneration of the p-phenylenediamine in a polyester material system, thereby promoting the long-term effective circulation effect of the p-phenylenediamine and the p-diphenol, effectively capturing the active free electrons in the polyester material system and inhibiting the continuous electron loss reaction of the polyester resin; and when the mass ratio of p-phenylenediamine to p-diphenol is 1.5:1, the polymer can effectively participate in a crosslinking system of the polyester composite material in a synergistic way, so that the intermolecular density is enhanced, the quantity and the free speed of free electrons are reduced, and the chemical solvent resistance of the material is effectively improved.
As a preferred embodiment, the elastic particles are modified polyurethane elastomer particles.
As a preferable scheme, the mass ratio of the elastic particles to the dihydric alcohol is 2-3: 7-8.
As a preferable scheme, the mass ratio of the elastic particles to the dihydric alcohol is 3:7.
as a preferred embodiment, the modified polyurethane elastomer particles are OBC modified TPU elastomer particles.
The preparation method of the OBC modified TPU elastomer particles comprises the following steps: (1) preparation of master batch: regulating the temperature of an internal mixer to 150-200 ℃, adding TPU elastomer when the temperature reaches a specified value, adding OBC copolymer after 10-15 minutes, banburying for 5-10 minutes, adding vulcanizing agent and vulcanization accelerator, dynamically vulcanizing for 8-10 minutes, taking out sizing material, tabletting by an open mill, preparing master batch for later use; (2) And (3) drying the master batch in a constant temperature oven at 100-140 ℃ for 1-3 hours, extruding by an extruder at 100-120 ℃ for granulating by a granulator, and grinding to the specified fineness to prepare the OBC modified TPU elastomer particles.
As a preferable embodiment, the average particle diameter of the bullet-modified polyurethane elastomer particles is 1000 to 2000 mesh.
As a preferred embodiment, the average particle diameter of the bullet-modified polyurethane elastomer particles is 1500 mesh.
In the application, the integral toughness and mechanical strength of the polyester resin material are effectively improved by adding the OBC modified TPU elastomer particles, and the thermoplastic polyurethane elastomer material has good surface tearing resistance. The applicant speculates that: the octene short-chain branched structure of the OBC copolymer can form a regular soft and hard block structure in the modification process of TPU particles, so that the composite material has a certain crystallinity, the modified composite particles can form a network structure formed by intertwining a large number of side chain groups in a polyester resin material, and the network structure can be used as physical crosslinking points of the polyester resin material in a tight crosslinking state; especially when the average particle diameter of the elastic modified polyurethane elastomer particles is 1500 meshes, the composite particles can also form a micropore structure in a microscopic state when the polyester material receives the action of external force, so that the elastic modified polyurethane elastomer particles can help to fill the cracks of the polyester material and form a filiform connection effect of an effective active group with the polyester, and the action of external force is effectively converted into a silver vein state again.
As a preferable embodiment, the catalyst is a titanium-based catalyst or a tin-based catalyst.
The second aspect of the present invention provides a method for preparing the high-toughness polyester resin material, comprising the steps of: (1) Firstly, placing a preset amount of dihydric alcohol, organic acid dibasic acid and 50wt% of catalyst into a high-temperature reaction kettle, and keeping the temperature at 180-220 ℃ for reaction for 4-5 hours; (2) Continuously adding carboxylic acid monomer, auxiliary agent, elastic particles and 50wt% of catalyst into a high-temperature reaction kettle, and keeping the temperature between 150 and 160 ℃ for 2.5 to 3.5 hours; (3) And (3) carrying out final polycondensation reaction on the product obtained in the step (2), wherein the reaction temperature is 200-220 ℃, the pressure is 2-5 mbar, and the reaction time is 4-5 hours.
The beneficial effects are that:
1. the high-toughness polyester resin material prepared by the invention has excellent biodegradability, and can effectively and greatly improve the toughness and mechanical strength of the polyester resin material through the synergistic effect of the elastomer material and the modified monomer, so that the mechanical strength and toughness of the polyester resin material are effectively expanded.
2. The amine and phenol auxiliary agents added into the high-toughness polyester resin material can effectively improve the oxidation resistance of the polyester resin material, and can also improve the long-term yellowing resistance and resin crosslinking effect of the polyester material through the synergistic effect of the amine and the phenol auxiliary agents, so that the service life and solvent resistance of the polyester material are improved.
3. According to the high-toughness polyester resin material prepared by the invention, through the synergistic effect of the carboxylic acid monomer and the elastomer material, the toughness of the biodegradable polyester resin material is effectively improved, the precipitation of the elastomer material is effectively avoided, and the storage and service life of the polyester resin material are prolonged.
Detailed Description
Example 1
Example 1 in a first aspect, a high toughness polyester resin material is provided, the raw materials comprising the following parts by weight: 35 parts of 1, 4-butanediol, 75 parts of phthalic acid, 15 parts of isosorbide-2, 5-dicarboxylic acid, 9 parts of p-phenylenediamine and p-diphenol (mass ratio 1.5:1), 15 parts of OBC modified TPU elastomer particles (1500 meshes), 4 parts of tetrabutyl titanate and 4 parts of dibutyltin diacetate.
In this example, the preparation process steps of the OBC modified TPU elastomer particles comprise the following steps (in parts by weight): (1) preparation of master batch: regulating the temperature of an internal mixer to 160 ℃, adding 50 parts of TPU elastomer when the temperature reaches a specified value, adding 10 parts of OBC copolymer after 12 minutes, banburying for 8 minutes, adding BIPB and trimethylolpropane trimethacrylate, dynamically vulcanizing for 8 minutes, taking out the sizing material, tabletting by an open mill, and preparing master batch for later use; (2) And (3) drying the master batch in a constant temperature oven at 130 ℃ for 2 hours, extruding by an extruder at the set temperature of 110 ℃, granulating by a granulator, and grinding to the specified fineness to prepare the OBC modified TPU elastomer particles.
In this example, the OBC is an olefin block copolymer product sold in the United states under the name 9530.
In this example, the TPU is a type 9385A TPU product sold by Bayer in Germany.
In the present embodiment of the present invention,
the second aspect of the present embodiment provides a method for preparing the high-toughness polyester resin material, which comprises the following steps: (1) Firstly, a predetermined amount of 1, 4-butanediol, phthalic acid and tetrabutyl titanate are put into a high-temperature reaction kettle, and the temperature is kept at 190 ℃ for reaction for 4.5 hours; (2) Continuously adding isosorbide-2, 5-dicarboxylic acid, p-phenylenediamine and p-diphenol, OBC modified TPU elastomer particles and dibutyltin diacetate into a high-temperature reaction kettle, and keeping the temperature at 155 ℃ for reaction for 3 hours; (3) And (3) carrying out final polycondensation reaction on the product obtained in the step (2), wherein the reaction temperature is 210 ℃, the pressure is 4mbar, and the reaction time is 4-5 hours.
Example 2
The specific implementation of this example is the same as example 1, except that: the particle size of the OBC modified TPU elastomer particles was on average 1000 mesh.
Comparative example 1
The specific embodiment of this comparative example is the same as example 1, except that: the isosorbide-2, 5-dicarboxylic acid is 5 parts.
Comparative example 2
The specific embodiment of this comparative example is the same as example 1, except that: p-phenylenediamine was not added and p-diphenol was 5 parts.
Comparative example 3
The specific embodiment of this comparative example is the same as example 1, except that: the OBC modified TPU elastomer particles were 400 mesh.
Evaluation of Performance
1. Mechanical properties: the polyester resin materials prepared in all examples and comparative examples were prepared into bars of 5cm x2cm, and the tensile strength and elongation at break of the bars were tested by a universal stretcher, 5 samples were tested in each example comparative example, and the average of the measured values is reported in table 1.
2. Chemical resistance: the polycarbonate materials prepared in each example and comparative example were prepared into corresponding test bars of 5cmx2cmx2cm, chemical agents (Banana BOAT Ultra Sport SPF) were coated on the surfaces of the bars during the tensile test, the stretching angle of the fixed curved surface was 20 °, and after 15 days, the number of cracks on the surfaces of the bars was observed, wherein 3 or less bars were A, 3 or less bars were B, and 6 or more bars were C.
TABLE 1
| Examples | Tensile strength MPa | Elongation at break% | Chemical resistance |
| Implementation of the embodimentsExample 1 | 38.7 | 657 | A |
| Example 2 | 37.8 | 648 | A |
| Comparative example 1 | 24.5 | 510 | B |
| Comparative example 2 | 26.7 | 499 | B |
| Comparative example 3 | 26.4 | 527 | C |
It can be known from examples 1-2, comparative examples 1-3 and table 1 that the high-toughness polyester resin material and the preparation method thereof provided by the invention have good rigidity, mechanical properties and chemical resistance, effectively enhance the toughness of the polyester elastomer, are suitable for popularization in the field of polyester resins, and have wide development prospects. Wherein example 1 obtained the best performance index under the factors of the best preparation raw material proportion and preparation process.
Claims (1)
1. A high-toughness polyester resin material is characterized in that: the raw materials comprise the following components in parts by weight: 35 parts of 1, 4-butanediol, 75 parts of phthalic acid, 15 parts of isosorbide-2, 5-dicarboxylic acid, 9 parts of p-phenylenediamine and hydroquinone, 15 parts of OBC modified TPU elastomer particles, 4 parts of tetrabutyl titanate and 4 parts of dibutyltin diacetate;
the mass ratio of the p-phenylenediamine to the hydroquinone is 1.5:1;
the average particle size of the OBC modified TPU elastomer particles is 1500 meshes;
the preparation method of the OBC modified TPU elastomer particles comprises the following steps of: (1) preparation of master batch: regulating the temperature of an internal mixer to 160 ℃, adding 50 parts of TPU elastomer when the temperature reaches a specified value, adding 10 parts of OBC copolymer after 12 minutes, banburying for 8 minutes, adding BIPB and trimethylolpropane trimethacrylate, dynamically vulcanizing for 8 minutes, taking out the sizing material, tabletting by an open mill, and preparing master batch for later use; (2) Drying the master batch in a constant temperature oven at 130 ℃ for 2 hours, extruding by an extruder at the set temperature of 110 ℃, granulating by a granulator, and then grinding to the specified fineness to prepare OBC modified TPU elastomer particles;
the preparation method of the high-toughness polyester resin material comprises the following steps: (1) Firstly, a predetermined amount of 1, 4-butanediol, phthalic acid and tetrabutyl titanate are put into a high-temperature reaction kettle, and the temperature is kept at 190 ℃ for reaction for 4.5 hours; (2) Continuously adding isosorbide-2, 5-dicarboxylic acid, p-phenylenediamine, hydroquinone, OBC modified TPU elastomer particles and dibutyltin diacetate into a high-temperature reaction kettle, and keeping the temperature at 155 ℃ for reaction for 3 hours; (3) And (3) carrying out final polycondensation reaction on the product obtained in the step (2), wherein the reaction temperature is 210 ℃, the pressure is 4mbar, and the reaction time is 4-5 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005325166A (en) * | 2004-05-12 | 2005-11-24 | Sumitomo Bakelite Co Ltd | Polyester resin sheet, laminated sheet of the same, and card given by using the same |
| CN110054764A (en) * | 2019-05-07 | 2019-07-26 | 安徽美佳新材料股份有限公司 | A kind of synthetic method of polyester resin |
| CN111116882A (en) * | 2020-01-03 | 2020-05-08 | 东华大学 | Full-biodegradable copolyester and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005325166A (en) * | 2004-05-12 | 2005-11-24 | Sumitomo Bakelite Co Ltd | Polyester resin sheet, laminated sheet of the same, and card given by using the same |
| CN110054764A (en) * | 2019-05-07 | 2019-07-26 | 安徽美佳新材料股份有限公司 | A kind of synthetic method of polyester resin |
| CN111116882A (en) * | 2020-01-03 | 2020-05-08 | 东华大学 | Full-biodegradable copolyester and preparation method and application thereof |
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