CN111925637B - Rapid-curing unsaturated polyester resin for vacuum introduction - Google Patents
Rapid-curing unsaturated polyester resin for vacuum introduction Download PDFInfo
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- CN111925637B CN111925637B CN202010759511.7A CN202010759511A CN111925637B CN 111925637 B CN111925637 B CN 111925637B CN 202010759511 A CN202010759511 A CN 202010759511A CN 111925637 B CN111925637 B CN 111925637B
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- unsaturated polyester
- polyester resin
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- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000004321 preservation Methods 0.000 claims description 17
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000006136 alcoholysis reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 2
- 239000003112 inhibitor Substances 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 238000009755 vacuum infusion Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000003085 diluting agent Substances 0.000 abstract description 4
- 125000004018 acid anhydride group Chemical group 0.000 abstract description 3
- 239000011152 fibreglass Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000011417 postcuring Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229940120693 copper naphthenate Drugs 0.000 description 2
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- VTWDKFNVVLAELH-UHFFFAOYSA-N methyl-p-benzoquinone Natural products CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-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
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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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)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a fast-curing unsaturated polyester resin for vacuum introduction, which comprises a matrix resin R1 and a compound accelerator E1, wherein the weight ratio of the matrix resin R1 to the compound accelerator E1 is 100:1 to 100:5. The matrix resin R1 comprises the following components in weight: 15-20% of PET bottle flakes, 23-28% of dihydric alcohol, 17-20% of unsaturated dibasic acid/anhydride, 0.01-0.03% of catalyst, 0.02-0.03% of first polymerization inhibitor and 36-40% of active diluent. The compound accelerator E1 comprises the following components in parts by weight: 91-93% of ionic accelerator, 5-7% of organic shielding agent and 1-2% of second polymerization inhibitor. The rapid-curing unsaturated polyester resin for the vacuum infusion molding process has shorter curing time and demolding time, and the product still maintains good mechanical strength.
Description
Technical Field
The invention belongs to the field of polyester resin manufacture, and particularly relates to a fast-curing unsaturated polyester resin for vacuum introduction.
Background
Glass fiber reinforced plastic composite materials are referred to as glass fiber reinforced plastics, and generally comprise a matrix material and a reinforcing material (such as glass fiber, carbon fiber, boron fiber, aramid fiber, aluminum oxide fiber, silicon carbide fiber and the like) which are formed by synthetic resin. The glass fiber reinforced plastic has the characteristics of light weight, high strength, corrosion resistance, ageing resistance, easy molding, heat resistance, insulation, long service life and the like.
The traditional unsaturated polyester resin glass fiber reinforced plastic is mainly manufactured by using a manual paste forming process, and the liquid unsaturated polyester resin is exposed to the air in a large area in the production process, so that the VOC emission is extremely high, and the health of workers is greatly endangered.
The vacuum leading-in forming process is a novel glass fiber reinforced plastic forming process, and has the characteristics of low pollution, high efficiency, high product quality stability and the like compared with the traditional high-pollution and manpower-intensive hand lay-up forming process. Because the negative pressure is needed to be formed in the mould by vacuumizing, the upper mould and the lower mould are needed to be closed, unsaturated polyester resin is not contacted with air in the process of introduction, VOC emission is zero in the process of forming, and the method is greatly improved on the physical health of workers and the pollution of the environment. However, the vacuum introducing and forming process needs one-step forming, so that the vacuum introducing and forming process is widely used for manufacturing large glass reinforced plastic parts, and is generally slow in post-curing and demoulding (more than 1.5 hours).
Disclosure of Invention
An object of the present invention is to provide an unsaturated polyester resin which can greatly reduce post-curing time, improve demolding efficiency and have high performance, aiming at the technical problems to be solved.
It is another object of the present invention to provide a process for producing the above unsaturated polyester resin.
In order to achieve the above object, the present invention provides a fast-curing unsaturated polyester resin for vacuum introduction, comprising a matrix resin R1 and a compounding accelerator E1, wherein the weight ratio of the matrix resin R1 to the compounding accelerator E1 is 100:1 to 100:5.
Preferably, the matrix resin R1 comprises the following components by weight: 15-20% of PET bottle flakes, 23-28% of dihydric alcohol, 17-20% of unsaturated dibasic acid/anhydride, 0.01-0.03% of catalyst, 0.02-0.03% of first polymerization inhibitor and 36-40% of active diluent.
More preferably, the PET bottle flakes are ordinary blue-white bottle flake grade PET bottle flakes.
More preferably, the unsaturated dibasic acid/anhydride is maleic anhydride.
More preferably, the dihydric alcohol is one or more of propylene glycol, diethylene glycol, dipropylene glycol and methyl propylene glycol.
More preferably, the catalyst is an organozinc-based catalyst or an organotin-based catalyst. More preferably, the catalyst is one or more of zinc acetate, di-n-butyltin dilaurate and stannous octoate.
More preferably, the first polymerization inhibitor is one or more of hydroquinone, methyl hydroquinone and p-benzoquinone. Further, the first polymerization inhibitor is preferably a combination of hydroquinone and methylhydroquinone.
More preferably, the reactive diluent is one or more of styrene and methyl styrene. Further, the reactive diluent is styrene.
Preferably, the compounding accelerator E1 comprises the following components by weight: 91-93% of ionic accelerator, 5-7% of organic shielding agent and 1-2% of second polymerization inhibitor.
More preferably, the ion accelerator is one or more of cobalt iso-octoate, potassium iso-octoate, copper naphthenate.
More preferably, the organic shielding agent is an amine-based organic accelerator including, but not limited to, one or more of N, N-dimethylaniline, triethanolamine, triethylenediamine.
More preferably, the second polymerization inhibitor is one or more of methyl hydroquinone and p-tert-butyl catechol.
In the invention, the high-activity high-strength unsaturated polyester resin matrix resin R1 has high curing reaction activity and contains terephthalic acid groups, can be quickly cured after resin gel, and has high strength after the glass fiber reinforced plastic product is cured; the compound accelerator E1 has the accelerating characteristics of adapting to different curing dosages of vacuum-introduced resin at different temperatures, and has the characteristics of long gel time and quick curing. The mixing of the matrix resin R1 and the compounding accelerator E1 in different proportions can realize good product performance. The organic shielding agent such as amine organic accelerator is adopted, the amine accelerator can form a coordination complex with the ionic accelerator, can rapidly shield the polymerization inhibitor in the resin, and can effectively catalyze and harden products in a hardening stage, greatly improve the post-curing speed, greatly reduce the demolding time (less than 0.5 hour), greatly improve the production efficiency, and is suitable for small products requiring high-speed curing and high performance, such as small carbon fiber automobile parts, pedal products and the like.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, 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.
Unless otherwise specified, the apparatus or reagents used in the examples are all conventional in the art and are commercially available. Unless otherwise indicated, all specific experimental operations referred to herein are understood or known by those skilled in the art according to common general knowledge or conventional technical means, and are not described in detail herein. For simplicity, some of the operations do not detail the parameters, steps, and instrumentation used for operation, it being understood that these are well known and reproducible by those skilled in the art.
Example 1
The PET type rapid curing unsaturated polyester resin applied to the vacuum lead-in molding process comprises the following two components:
1. component A: the formula of the high-activity high-strength unsaturated polyester resin matrix resin R1 is as follows:
2. component B: the formula of the compound accelerator E1 is as follows:
the preparation method comprises the following steps:
(1) PET alcoholysis: PET bottle flakes, dihydric alcohol and stannous chloride are put into a four-neck flask, and the four-neck flask, a mechanical stirrer and a reflux condenser are arranged on a heating sleeve. Heating to 180 ℃, then slowly heating to 220 ℃, and observing whether the temperature of the distillation head rises or not in the heating process; and (3) carrying out heat preservation reaction for 3-4 h, paying attention to the alcoholysis speed of PET in the heat preservation process, obtaining a reaction end point when PET particles are not reacted, calculating the yield, and measuring the acid value (2 < Av < 5).
(2) And (3) a synthesis stage: adding dibasic acid into the four-neck flask according to the formula, heating to 150 ℃, slowly heating to water outlet, and preserving heat for 0.5h at the water outlet temperature; after the heat preservation is finished, the temperature is increased to 210 ℃ according to 10 ℃/h, the heat preservation is carried out for 4 to 5 hours, when the measured acid value is less than 35 (namely Av is less than 30), the temperature is reduced to 160 ℃, hydroquinone and methyl hydroquinone are added, the temperature is continuously reduced to 120 ℃, and styrene is added for dilution. Stirring uniformly. The appearance was observed and the viscosity was measured and adjusted to 180 to 220mPas.
(3) Mixing the matrix resin R1 and the compounding accelerator E1 in a weight ratio of 100:1, and stirring for 0.5h until uniform. The fast curing vacuum infusion resin is prepared.
Example 2
The PET type rapid curing unsaturated polyester resin applied to the vacuum lead-in molding process comprises the following two components:
1. component A: the formula of the high-activity high-strength unsaturated polyester resin matrix resin R1 is as follows:
2. component B: the formula of the compound accelerator E1 is as follows:
the preparation method comprises the following steps:
(1) PET alcoholysis: PET bottle flakes, dihydric alcohol and stannous chloride are put into a four-neck flask, and the four-neck flask, a mechanical stirrer and a reflux condenser are arranged on a heating sleeve. Heating to 180 ℃, then slowly heating to 220 ℃, and observing whether the temperature of the distillation head rises or not in the heating process; and (3) carrying out heat preservation reaction for 3-4 h, paying attention to the alcoholysis speed of PET in the heat preservation process, obtaining a reaction end point when PET particles are not reacted, calculating the yield, and measuring the acid value (2 < Av < 5).
(2) And (3) a synthesis stage: adding dibasic acid into the four-neck flask according to the formula, heating to 150 ℃, slowly heating to water outlet, and preserving heat for 0.5h at the water outlet temperature; after the heat preservation is finished, the temperature is increased to 210 ℃ according to 10 ℃/h, the heat preservation is carried out for 4 to 5 hours, when the measured acid value is less than 35 (namely Av is less than 30), the temperature is reduced to 160 ℃, hydroquinone and methyl hydroquinone are added, the temperature is continuously reduced to 120 ℃, and styrene is added for dilution. Stirring uniformly. The appearance was observed and the viscosity was measured and adjusted to 180 to 220mPas.
(3) Mixing the matrix resin R1 and the compounding accelerator E1 in a weight ratio of 100:3, and stirring for 0.5h until uniform. The fast curing vacuum infusion resin is prepared.
Example 3
The PET type rapid curing unsaturated polyester resin applied to the vacuum lead-in molding process comprises the following two components:
1. component A: the formula of the high-activity high-strength unsaturated polyester resin matrix resin R1 is as follows:
2. component B: the formula of the compound accelerator E1 is as follows:
the preparation method comprises the following steps:
(1) PET alcoholysis: PET bottle flakes, dihydric alcohol and stannous chloride are put into a four-neck flask, and the four-neck flask, a mechanical stirrer and a reflux condenser are arranged on a heating sleeve. Heating to 180 ℃, then slowly heating to 220 ℃, and observing whether the temperature of the distillation head rises or not in the heating process; and (3) carrying out heat preservation reaction for 3-4 h, paying attention to the alcoholysis speed of PET in the heat preservation process, obtaining a reaction end point when PET particles are not reacted, calculating the yield, and measuring the acid value (2 < Av < 5).
(2) And (3) a synthesis stage: adding dibasic acid into the four-neck flask according to the formula, heating to 150 ℃, slowly heating to water outlet, and preserving heat for 0.5h at the water outlet temperature; after the heat preservation is finished, the temperature is increased to 210 ℃ according to 10 ℃/h, the heat preservation is carried out for 4 to 5 hours, when the measured acid value is less than 35 (namely Av is less than 30), the temperature is reduced to 160 ℃, hydroquinone and methyl hydroquinone are added, the temperature is continuously reduced to 120 ℃, and styrene is added for dilution. Stirring uniformly, observing appearance, measuring viscosity, and adjusting to 180-220 mPas.
(3) Mixing the matrix resin R1 and the compounding accelerator E1 in a weight ratio of 100:5, and stirring for 0.5h until uniform. The fast curing vacuum infusion resin is prepared.
Comparative example
The PET type rapid curing unsaturated polyester resin applied to the vacuum lead-in molding process comprises the following two components:
1. component A: the formula of the high-activity high-strength unsaturated polyester resin matrix resin R1 is as follows:
2. component B: the accelerator comprises the following components in percentage by weight:
n, N-diethylaniline 0.2g
Copper naphthenate 0.002g
The preparation method comprises the following steps:
(1) PET alcoholysis: PET bottle flakes, dihydric alcohol and stannous chloride are put into a four-neck flask, and the four-neck flask, a mechanical stirrer and a reflux condenser are arranged on a heating sleeve. Heating to 180 ℃, then slowly heating to 220 ℃, and observing whether the temperature of the distillation head rises or not in the heating process; and (3) carrying out heat preservation reaction for 3-4 h, paying attention to the alcoholysis speed of PET in the heat preservation process, obtaining a reaction end point when PET particles are not reacted, calculating the yield, and measuring the acid value (2 < Av < 5).
(2) And (3) a synthesis stage: adding dibasic acid into the four-neck flask according to the formula, heating to 150 ℃, slowly heating to water outlet, and preserving heat for 0.5h at the water outlet temperature; after the heat preservation is finished, the temperature is increased to 210 ℃ according to 10 ℃/h, the heat preservation is carried out for 4 to 5 hours, when the measured acid value is less than 35 (namely Av is less than 30), the temperature is reduced to 160 ℃, hydroquinone and methyl hydroquinone are added, the temperature is continuously reduced to 120 ℃, and styrene is added for dilution. Stirring uniformly, observing appearance, measuring viscosity, and adjusting to 180-220 mPas.
(3) Mixing the matrix resin R1 and the accelerator in a weight ratio of 100:1, and stirring for 0.5h to be uniform. The fast curing vacuum infusion resin is prepared.
Resin Performance test
Cutting four 300 mm/300 mm LT800C450 type composite felts, horizontally placing on a flat vacuum introducing mold, pressing and forming a product by adopting a bag film method vacuum introducing forming process, and vacuumizing.
500g of the quick-setting vacuum infusion resins obtained in examples 1, 2 and 3, the resin of the comparative example and the 191 general-purpose resin (1% by weight of commercially available accelerator E01 were added in advance), 2% by weight of commercially available curing agent ME01 was added at 30℃at room temperature, and the resulting mixture was introduced into the above-mentioned mold, respectively. After the mold is fully filled with resin by vacuum introduction, the introduction is stopped, and the resin is waited for gelling, hardening, curing and demolding. The introduction time, gel time, release time, and mechanical properties of the product were measured. The results are shown in Table 1.
Table 1: results of resin Performance test
| Example 1 | Example 2 | Example 3 | 191 general purpose resin | Comparative example | |
| viscosity/mPas | 208 | 206 | 199 | 300 | 201 |
| Lead-in time/min | 6 | 5.5 | 5.8 | 11 | 15 |
| Gel time/min | 8 | 7 | 8 | 8 | 7 |
| Demolding time/min | 20 | 19 | 18 | 120 | 80 |
| Demolding hardness/HBa | 25 | 20 | 30 | 15 | 18 |
| Article of manufactureTensile Strength/MPa | 420 | 413 | 405 | 360 | 400 |
| Tensile modulus/GPa of an article | 2.05 | 2.02 | 2.03 | 1.98 | 2.01 |
| Flexural Strength of article/MPa | 611 | 605 | 655 | 455 | 580 |
| Flexural modulus/GPa of an article | 2.1 | 2.08 | 2.09 | 2.05 | 2.06 |
| Product impact toughness/kJ/m 2 | 239 | 259 | 240 | 227 | 230 |
From the above test results, it is seen that the rapid-curing unsaturated polyester resin for vacuum infusion molding process of the present invention has a shorter curing time and demolding time than the existing products, and the product maintains good mechanical strength.
Claims (1)
1. The PET type rapid curing unsaturated polyester resin applied to the vacuum introduction molding process consists of a component A and a component B, and is characterized in that the component A is a high-activity high-strength unsaturated polyester resin matrix resin R1, and the formula is as follows:
the component B is a compound accelerator E1, and the formula is as follows:
the preparation method comprises the following steps:
(1) PET alcoholysis: adding PET bottle flakes, dihydric alcohol and stannous chloride, heating to 180 ℃, then slowly heating to 220 ℃, and observing whether the temperature of the distillation head rises or not in the heating process; keeping the temperature for 3-4 h, paying attention to the alcoholysis speed of PET in the process of keeping the temperature, taking the reaction as a reaction end point when PET particles are not reacted, calculating the yield, and measuring the acid value of the product;
(2) And (3) a synthesis stage: adding dibasic acid according to the formula, heating to 150 ℃, slowly heating to water outlet, and preserving heat for 0.5h at the water outlet temperature; heating to 210 ℃ at 10 ℃/h after heat preservation, preserving heat for 4-5 h, cooling to 160 ℃ when the measured acid value is less than 35, adding hydroquinone, methyl hydroquinone, continuously cooling to 120 ℃, and adding styrene for dilution; stirring uniformly, observing the appearance, measuring the viscosity of the mixture, and adjusting the viscosity to 180-220 mPas;
(3) Mixing the matrix resin R1 and the compounding accelerator E1 in a weight ratio of 100:5, and stirring for 0.5h to be uniform to obtain the PET type rapidly-cured unsaturated polyester resin.
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| CN105542133A (en) * | 2016-01-28 | 2016-05-04 | 常州天马集团有限公司（原建材二五三厂） | Specific unsaturated polyester resin for manufacturing metal polished particles and preparation method of specific unsaturated polyester resin |
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| JPH06200002A (en) * | 1993-01-06 | 1994-07-19 | Showa Highpolymer Co Ltd | Production of unsaturated polyester |
| JP2003039567A (en) * | 2001-07-27 | 2003-02-13 | Hitachi Chem Co Ltd | Method for manufacturing fiber reinforced plastic molded article |
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