CN116239780B - Preparation method of modified vinyl ester resin - Google Patents
Preparation method of modified vinyl ester resin Download PDFInfo
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- CN116239780B CN116239780B CN202111481699.4A CN202111481699A CN116239780B CN 116239780 B CN116239780 B CN 116239780B CN 202111481699 A CN202111481699 A CN 202111481699A CN 116239780 B CN116239780 B CN 116239780B
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- 229920005989 resin Polymers 0.000 title claims abstract description 41
- 239000011347 resin Substances 0.000 title claims abstract description 41
- 229920001567 vinyl ester resin Polymers 0.000 title claims abstract description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229920002545 silicone oil Polymers 0.000 claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 30
- 239000012948 isocyanate Substances 0.000 claims description 19
- 150000002513 isocyanates Chemical class 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 abstract description 14
- 239000011159 matrix material Substances 0.000 abstract description 6
- -1 polydimethylsiloxane Polymers 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000012745 toughening agent Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- 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
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a preparation method of modified vinyl ester resin. The method comprises the steps of (1) reacting epoxy-terminated silicone oil with organic carboxylic acid and then reacting with diisocyanate to obtain modified silicone oil with an isocyanate group as a terminal group, (2) reacting epoxy resin with unsaturated monoacid and then adding a cross-linking agent, (3) reacting the product obtained in the step (2) with the modified silicone oil in the step (1) to obtain the modified vinyl ester resin. The invention adopts the linear polydimethylsiloxane with the end group of epoxy functional group as the toughening agent, can be used as a modified reactive site, and has good molecular chain flexibility and good toughening effect. The modified silicone oil with the synthesized end group being isocyanate group reacts with vinyl ester resin, so that the product quality is stable, the compatibility of the modified resin and matrix resin is good, and the toughening modification effect is better.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a synthetic method of modified vinyl ester resin.
Background
The vinyl ester resin is prepared by ring-opening addition reaction of epoxy resin and monounsaturated carboxylic acid, and the product is dissolved in unsaturated polymerizable monomer. Under the initiation of organic peroxide, the cross-linking curing can be performed, and the cured product has high mechanical strength, excellent chemical resistance and hydrolysis resistance stability, and has wide application in the fields of chemical industry, metallurgy, papermaking, aerospace and the like. However, vinyl ester resin belongs to thermosetting resin cured by free radicals, has high crosslinking density, causes high resin brittleness, and is difficult to meet the requirement of certain special products on the toughness of matrix resin, so that the brittleness of the vinyl ester resin is improved, and the vinyl ester resin has important significance for improving the performance of the existing products and widening the application field.
Patent CN103304749a discloses a method for modifying vinyl ester resin, which adopts long-chain saturated diacid to partially replace unsaturated monobasic acid to react with epoxy resin, introduces flexible diacid molecular long chain into molecular main chain, and improves flexibility of molecular chain. Patent CN1793196a discloses a method for modifying vinyl ester resin, which adopts carboxyl-terminated liquid nitrile rubber, and reacts with unsaturated monocarboxylic acid, saturated dibasic fatty acid and epoxy resin in the presence of catalyst, and the nitrile rubber modified vinyl ester resin, but the unreacted nitrile rubber and styrene solvent have poor intersolubility, so delamination is easy to cause, and the stability of the final product is affected. Zhou Runpei (glass fibre reinforced plastics/composite materials, 2000 (2): 21-22) and the like introduce flexible isocyanate groups into the molecular structure of vinyl ester resins, so that polyurethane groups are contained in the molecular chain of the synthetic resin, but the improvement of the toughness of the resin is limited due to the adoption of isocyanate monomer modification.
Disclosure of Invention
The invention aims to provide a preparation method of modified vinyl ester resin, which is used for improving the toughness of the resin, has the advantages of simple operation, less side reaction, no byproduct generation, high toughness and stable quality, and the obtained product can meet the requirement of fan blades, sports equipment, petrochemical equipment and the like on the toughness of matrix resin.
The invention provides a preparation method of modified vinyl ester resin, which comprises the following steps:
(1) Adding a catalyst A into epoxy-terminated silicone oil and organic carboxylic acid, reacting at 90-130 ℃, stopping the reaction when the acid value is reduced to below 12mgKOH/g, cooling to room temperature, adding diisocyanate and a catalyst B, reacting at 70-90 ℃, and obtaining modified silicone oil with an isocyanate group as a terminal group when the isocyanate group content is unchanged;
(2) Reacting epoxy resin with unsaturated monoacid in the presence of a catalyst A and a polymerization inhibitor at 90-130 ℃ until the acid value is reduced to below 12mgKOH/g as a reaction end point, adding a cross-linking agent, and stirring and mixing uniformly;
(3) And (3) reacting the product obtained in the step (2) with the modified silicone oil obtained in the step (1) in the presence of a catalyst B at 70-90 ℃ to determine the isocyanate content to be 0, thereby obtaining the modified vinyl ester resin.
The molecular weight of the epoxy silicone oil at the end of the step (1) is 500-6000. For example JF-852 series epoxy silicone oil-1000, epoxy silicone oil-2000 and epoxy silicone oil-3000 of Jieshikari of Wuhan Hua Xiangke.
The organic carboxylic acid is one or more of acetic acid, propionic acid or butyric acid.
The molar ratio of the epoxy-terminated silicone oil to the organic carboxylic acid is 1:2.
The catalyst A refers to an amine organic base catalyst such as tributylamine, triethanolamine, triethylamine and the like or a reducing salt catalyst such as quaternary ammonium salt and the like, and one or more of benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetrabutyl ammonium bromide, benzyl triethyl ammonium bromide and the like.
In the step (1) according to the invention, the catalyst A is used in an amount of 0.1 to 2% by weight, based on the sum of the weights of the terminal epoxy silicone oil and the organic carboxylic acid.
The diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate.
The catalyst B is dibutyl tin dilaurate and/or stannous octoate.
In the step (1) according to the invention, the catalyst B is used in an amount of 0.01 to 0.5% by weight, based on the sum of the weights of the terminal epoxy silicone oil and the organic carboxylic acid.
In the step (1), the molar ratio of the dosage of diisocyanate to the dosage of epoxy silicone oil is 2:1.
The epoxy resin in the step (2) is one of bisphenol A epoxy resin E-44, E-51 or E-54.
The unsaturated monocarboxylic acid is one or more of acrylic acid, methacrylic acid or trans-2-butenoic acid.
The polymerization inhibitor is one or more of hydroquinone, p-tert-butyl catechol, p-benzoquinone, alkyl p-benzoquinone, catechol, tetrachlorobenzoquinone and the like.
In the step (2), the epoxy resin is used in an amount of 35-48%, the unsaturated monoacid is used in an amount of 10-28% and the crosslinking agent is used in an amount of 35-45% based on the sum of the weights of the epoxy resin, the unsaturated monoacid and the crosslinking agent.
In the step (2), the dosage of the catalyst A is 0.1-2%, and the dosage of the polymerization inhibitor is 0.01-0.3%, based on the weight sum of the epoxy resin, the unsaturated monobasic acid and the crosslinking agent.
The cross-linking agent is one or more of styrene, p-methylstyrene, alpha-methylstyrene, methyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, diallyl isophthalate and diallyl terephthalate.
In the step (3), the amount of the modified silicone oil in the step (1) is 5-20% based on the sum of the weights of the epoxy resin, the unsaturated monoacid, the cross-linking agent and the modified silicone oil.
In the step (3), the amount of the catalyst B is 0.01 to 0.5 percent based on the weight sum of the epoxy resin, the unsaturated monobasic acid, the cross-linking agent and the modified silicone oil.
The preparation method is simple to operate, does not generate byproducts, meets the requirement of certain materials on the toughness of matrix resin, and has the following advantages:
① Linear polydimethylsiloxane with end groups of epoxy functional groups is used as a toughening agent, and the end groups of the linear polydimethylsiloxane are active epoxy groups and can be used as modified reactive sites. Because the bond angle of Si-O-Si is larger than that of C-C bond, the bond length is larger, so that the internal rotation resistance is smaller, the molecular chain flexibility is good, and the toughening effect is good.
② The modified silicone oil with the synthesized end group being isocyanate group reacts with vinyl ester resin, so that the product quality is stable, the compatibility of the modified resin and matrix resin is good, and the toughening modification effect is better.
Detailed Description
The invention will now be described in detail with reference to specific embodiments in which the components are in mass percent unless specifically indicated.
Example 1:
(1) 500g of epoxy silicone oil with molecular weight of 1000 is added into a three-neck flask, 60g of acetic acid and 3.36g of benzyl triethyl ammonium chloride are added, stirring is started, the temperature is raised to 100 ℃, the reaction is kept at a temperature, the acid value is measured every 1 hour, when the acid value is reduced to 12mgKOH/g, the reaction product is cooled to room temperature as a reaction end point, 174.2g of toluene diisocyanate and 0.17g of dibutyl tin dilaurate are added, the temperature is raised to 75 ℃ for heat-preserving reaction, the isocyanate content is measured every 30 minutes, and when the isocyanate content is kept unchanged, the reaction end point is reached, so that the modified silicone oil with the end group being an isocyanate group is obtained.
(2) 460G of epoxy resin E-44 and 182.98g of methacrylic acid, 5.36g of tetraethylammonium chloride and 0.43g of p-benzoquinone are added into the other three-neck flask, stirring is started, the temperature is raised to 110 ℃, the temperature is kept for reaction, the acid value is measured every one hour, 428.7g of styrene is added when the acid value is lower than 12mgKOH/g as the reaction end point, and stirring and mixing are uniform.
(3) And (3) cooling the reaction product to room temperature, adding 56.4g of the product obtained in the step (1), adding 1.13g of dibutyltin dilaurate, heating to about 70 ℃, measuring the isocyanate content once every 30 minutes, and obtaining the modified vinyl ester resin when the isocyanate content is zero and the reaction end point is reached.
Example 2:
(1) 600g of epoxy silicone oil with molecular weight of 2000 is added into a three-neck flask, 44.5g of propionic acid and 3.87g of tetrabutylammonium bromide are added, stirring is started, the temperature is raised to about 105 ℃, the reaction is kept at a constant temperature, the acid value is measured every 1 hour, when the acid value is reduced to 12mgKOH/g, the reaction is stopped, the reaction product is cooled to room temperature, 150.2g of diphenylmethane diisocyanate is added, 0.32g of stannous octoate is heated to about 70 ℃, the isocyanate content is measured every 30 minutes, and when the isocyanate content is unchanged, the end point of the reaction is reached, and the modified silicone oil with the end group of isocyanate group is obtained.
(2) 400G of epoxy resin E-51 and 154.3g of acrylic acid, 4.62g of benzyl triethyl ammonium bromide and 0.46g of catechol are added into another three-neck flask, stirring is started, the temperature is raised to about 115 ℃, the reaction is kept at a temperature, the acid value is measured every one hour, when the acid value is lower than 12mgKOH/g, the reaction end point is the acid value, 300g of methyl styrene and 69.5g of methyl acrylate are added, and stirring and mixing are uniform.
(3) And (3) cooling the reaction product to room temperature, adding 102.65g of the product obtained in the step (1), adding 2.05g of stannous octoate, heating to about 75 ℃, measuring the isocyanate content once every 30 minutes, and reaching the reaction end point when the isocyanate content is zero to obtain the modified vinyl ester resin.
Example 3:
(1) 1000g of epoxy silicone oil with molecular weight of 3000 is added into a three-neck flask, 58.7g of butyric acid and 5.29g of triethanolamine are added, stirring is started, the temperature is raised to about 110 ℃, the thermal insulation reaction is carried out, the acid value is measured every 1 hour, the reaction is stopped when the acid value is reduced to 12mgKOH/g, the reaction product is cooled to room temperature, 116.1g of toluene diisocyanate and 0.21g of dibutyl tin dilaurate are added, the temperature is raised to 75 ℃, the isocyanate content is measured every 30 minutes, and when the isocyanate content is unchanged, the end point of the reaction is reached, and the modified silicone oil with the end group being an isocyanate group is obtained.
(2) 700G of epoxy resin E-54 and 361.2g of methacrylic acid, 8.84g of triethanolamine and 1.06g of tetrachlorobenzoquinone are added into another three-neck flask, stirring is started, the temperature is raised to 115 ℃, the temperature is kept for reaction, the acid value is measured every one hour, when the acid value is lower than 12mgKOH/g, the reaction is stopped, 400g of p-methylstyrene and 307.5g of methyl methacrylate are added, and stirring and mixing are carried out uniformly.
(3) And (3) cooling the reaction product to room temperature, adding 312.12g of the product obtained in the step (1), adding 4.16g of dibutyltin dilaurate, starting stirring, heating to about 70 ℃, measuring the content of isocyanate every 30 minutes, and obtaining the modified vinyl ester resin when the content of isocyanate is zero.
Example 4:
(1) 700g of epoxy silicone oil with molecular weight of 1000, 103.7g of propionic acid and 5.63g of benzyl triethyl ammonium chloride are added into a three-neck flask, stirring is started, the temperature is raised to about 115 ℃, the reaction is kept at a temperature, the acid value is measured every 1 hour, the reaction is stopped when the acid value is reduced to 12mgKOH/g, the reaction product is cooled to room temperature, 243.8g of toluene diisocyanate is added, 0.56g of dibutyl tin dilaurate is added, stirring is started, the temperature is raised to 75 ℃, the isocyanate content is measured every 30 minutes, and when the isocyanate content is unchanged, the reaction end point is reached, so that the modified silicone oil with the end group being isocyanate group is obtained.
(2) Into another three-necked flask, 800g of epoxy resin E-51,308.57g of acrylic acid, 11.09g of benzyltriethylammonium chloride and 1.48g of hydroquinone were charged, and stirring was started and the temperature was raised to 115 ℃. The reaction was kept at a constant temperature, the acid value was measured every one hour, and when the acid value was reduced to 12mgKOH/g, the reaction was terminated, 500g of p-methylstyrene and 239g of methyl acrylate were added and stirred uniformly.
(3) Cooling the reaction product to room temperature, adding 461.9g of the product obtained in the step (1), 6.93g of dibutyltin dilaurate, heating to 70 ℃, measuring the isocyanate content once every 30 minutes, and reaching the reaction end point when the isocyanate content is zero to obtain the modified resin.
Comparative example 5:
460g of bisphenol A type epoxy resin, 182.98g of methacrylic acid, 56.4g of sebacic acid, 5.36g of tetraethylammonium chloride and 0.43g of p-benzoquinone are added into a three-neck flask, stirring is started, the temperature is gradually increased, the reaction temperature is controlled to react at 110 ℃, and the acid value is measured once every one hour until the acid value is reduced to below 12 mgKOH/g. And cooling the reaction product to about 100 ℃, adding 428.7g of styrene, and uniformly stirring to obtain the modified resin.
Comparative example 6:
460g of epoxy resin E-44 and 182.98g of methacrylic acid, 5.36g of tetraethylammonium chloride and 0.43g of p-benzoquinone are added into a three-neck flask, stirring is started, the temperature is raised to 110 ℃, the temperature is kept for reaction, the acid value is measured once every one hour, and the acid value is the end point of the reaction when the acid value is lower than 12 mgKOH/g. 56.4g of epoxy silicone oil with molecular weight of 1000 is added, 428.7g of styrene is added, and the mixture is stirred and mixed uniformly to obtain the modified resin.
The properties of the products of the examples and the comparative examples are shown in Table 1.
Table 1 product properties of examples, comparative examples
The modified resin has the tensile strength of 65-75MPa, the tensile modulus of 2500-3500MPa, the bending strength of 100-120MPa, the elongation at break of 15-25%, the impact strength of 30-45kJ/m 2, and compared with the unmodified resin, the toughness of the resin is obviously improved, and the requirement of materials such as wind power equipment, sports equipment, petrochemical equipment and the like on the toughness of matrix resin is met.
Claims (10)
1. A method for preparing a modified vinyl ester resin, comprising the steps of:
(1) Adding a catalyst A into epoxy-terminated silicone oil and organic carboxylic acid, reacting at 90-130 ℃, stopping the reaction when the acid value is reduced to below 12mgKOH/g, cooling to room temperature, adding diisocyanate and a catalyst B, reacting at 70-90 ℃, and obtaining modified silicone oil with an isocyanate group as a terminal group when the isocyanate group content is unchanged;
(2) Reacting epoxy resin with unsaturated monoacid in the presence of a catalyst A and a polymerization inhibitor at 90-130 ℃ until the acid value is reduced to below 12mgKOH/g as a reaction end point, adding a cross-linking agent, and stirring and mixing uniformly;
(3) And (3) reacting the product obtained in the step (2) with the modified silicone oil obtained in the step (1) in the presence of a catalyst B at 70-90 ℃ to determine the isocyanate content to be 0, thereby obtaining the modified vinyl ester resin.
2. The method according to claim 1, wherein the molecular weight of the epoxy-terminated silicone oil of step (1) is 500 to 6000.
3. The method of claim 1, wherein the organic carboxylic acid is one or more of acetic acid, propionic acid, and butyric acid.
4. The method according to claim 1, wherein the molar ratio of the epoxy-terminated silicone oil to the organic carboxylic acid is 1:2.
5. The process of claim 1 wherein the diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate.
6. The method of claim 1, wherein the epoxy resin in step (2) is one of bisphenol a epoxy resin E-44, E-51 or E-54.
7. The method of claim 1, wherein the unsaturated monocarboxylic acid is one or more of acrylic acid, methacrylic acid, or trans-2-butenoic acid.
8. The method according to claim 1, wherein in the step (2), the epoxy resin is used in an amount of 35 to 48%, the unsaturated monoacid is used in an amount of 10 to 28%, and the crosslinking agent is used in an amount of 35 to 45% based on the sum of the weights of the epoxy resin, the unsaturated monoacid, and the crosslinking agent.
9. The method according to claim 1, wherein in the step (3), the modified silicone oil of the step (1) is used in an amount of 5 to 20% based on the sum of the weights of the epoxy resin, the unsaturated monobasic acid, the crosslinking agent and the modified silicone oil.
10. The method of claim 1, wherein the cross-linking agent is one or more of styrene, para-methylstyrene, alpha-methylstyrene, methyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, diallyl isophthalate, diallyl terephthalate.
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| CN101974143A (en) * | 2010-10-14 | 2011-02-16 | 华南理工大学 | Organic silicon modified epoxy acrylate aqueous dispersion and preparation method thereof |
| CN102993375A (en) * | 2011-09-13 | 2013-03-27 | 德沃特化学新材料南通有限公司 | Elastomer toughening material and its synthetic method |
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| CN102993375A (en) * | 2011-09-13 | 2013-03-27 | 德沃特化学新材料南通有限公司 | Elastomer toughening material and its synthetic method |
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