CN112940263A - Vinyl resin, preparation method thereof and thickened vinyl resin composition - Google Patents
Vinyl resin, preparation method thereof and thickened vinyl resin composition Download PDFInfo
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- CN112940263A CN112940263A CN202110216776.7A CN202110216776A CN112940263A CN 112940263 A CN112940263 A CN 112940263A CN 202110216776 A CN202110216776 A CN 202110216776A CN 112940263 A CN112940263 A CN 112940263A
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- diisocyanate
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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Abstract
The invention relates to a vinyl resin and a preparation method thereof, and a thickened vinyl resin composition, wherein dibasic acid reacts with epoxy resin to obtain a carboxyl-terminated epoxy polymer, the carboxyl-terminated epoxy polymer reacts with polyurethane to obtain a vinyl resin with two terminal carboxyl groups and a side chain with unsaturated double bonds, and the vinyl resin, an active diluent and carboxyl-terminated unsaturated polyester form the thickened vinyl resin composition. The vinyl resin provided by the invention has excellent crosslinking property and compatibility with an active diluent, and the thickened vinyl resin composition has good thickening property and excellent mechanical property after thickening.
Description
Technical Field
The invention belongs to the technical field of resin, and particularly relates to vinyl resin, a preparation method thereof and a thickened vinyl resin composition.
Background
Vinyl resins are typically prepared from epoxy resins by chain extension with bisphenol a or fumaric acid followed by capping with an unsaturated mono-acid. For convenience of construction, a reactive diluent is usually added to prepare a liquid resin with storage stability, and a peroxy compound is added to initiate polymerization before construction.
Glass fiber and filler are usually added to enhance the mechanical properties of liquid vinyl resin, but the vinyl resin reinforced by glass fiber and filler needs to have higher viscosity, for example, in the SMC molding process, the vinyl resin is difficult to flow like rubber at room temperature and has ductility, otherwise the liquid vinyl resin is easy to flow, and the glass fiber and the filler are separated from the resin after being injected into a mold, so that the molding is difficult, and the thickening property of the vinyl resin is needed.
In the prior art, the vinyl resin is thickened by the reaction of anhydride and hydroxyl on a side chain of the vinyl resin, so that the side chain of the vinyl resin is provided with carboxyl, and then alkaline earth metal oxide reacts with the carboxyl to form macromolecules with a cross-linked network structure, thereby achieving the thickening effect. However, since the molecular weight of the vinyl resin is small, intramolecular coupling between the side chain carboxyl group in the molecule and the alkaline earth metal oxide is easily formed, and intermolecular coupling is offset, the molecular weight cannot be rapidly increased, and thus the thickening effect of the vinyl resin with the structure is weak.
Disclosure of Invention
The invention aims to provide a vinyl resin, and a vinyl resin composition composed of the vinyl resin has good thickening property and excellent mechanical property after thickening.
The invention provides a vinyl resin, two molecular terminals of which are carboxyl groups, and a side chain of which is provided with unsaturated double bonds, wherein the structural formula is as follows:
further, the raw materials used in the preparation method of the vinyl resin comprise the following components in percentage by weight: basic epoxy: 30-50wt%, bisphenol A: 0-30wt%, dibasic acid: 3-30wt%, styrene: 20-60 wt%; 5-30wt% of a monobasic acid containing a carbon-carbon double bond.
In addition, the present invention also provides a method for preparing the vinyl resin as described above, which comprises the steps of:
(1) and reacting the dibasic acid with epoxy resin to prepare the carboxyl-terminated polyepoxy polymer, wherein the epoxy resin is basic epoxy or bisphenol A type epoxy resin prepared by chain extension of the basic epoxy by bisphenol A.
(2) And (2) reacting the carboxyl-terminated epoxy polymer prepared in the step (1) with polyurethane to prepare the vinyl resin.
Further, in the step (1), the carboxyl-terminated polyepoxy polymer is prepared by using dibasic acid and epoxy resin in the presence of a unit acid containing a carbon-carbon double bond.
Furthermore, the unit acid containing the carbon-carbon double bond is one or more of acrylic acid, methacrylic acid, 2-butenoic acid and cinnamic acid.
Further, in the step (1), the dibasic acid is one or more of adipic acid, succinic acid, fumaric acid and succinic acid.
Further, the epoxy resin in the step (1) is a compound represented by the following formula (1) or formula (2):
formula (1)
Formula (2)
Further, in the step (2), the polyurethane is a polymer of diisocyanate and hydroxy (meth) acrylate; the diisocyanate is one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene-2, 4-diisocyanate (2, 4-TDI), toluene-2, 6-diisocyanate (2, 6-TDI), 4 '-diphenylmethane diisocyanate (MDI) and hydrogenated 4, 4' -diphenylmethane diisocyanate (H12 MDI); the hydroxyl (methyl) acrylate is one or more of hydroxyethyl (methyl) acrylate and hydroxypropyl (methyl) acrylate.
Namely, the polyurethane of the present invention as described above has the following structure:
the invention also provides a thickened vinyl resin composition which comprises the vinyl resin, a reactive diluent and carboxyl-terminated unsaturated polyester.
Wherein the active diluent is one or more of styrene, vinyl toluene, divinylbenzene and acrylate.
In addition, the carboxyl-terminated unsaturated polyester has the number average molecular weight of more than 4000 and is formed by polymerizing dibasic acid or dibasic anhydride and dihydric alcohol; the dibasic acid is one or more of adipic acid, succinic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid and maleic acid; the dibasic acid anhydride is one or more of succinic anhydride, phthalic anhydride and maleic anhydride; the dihydric alcohol is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, butanediol, neopentyl glycol, 2-methyl-1, 3-propylene glycol, diethylene glycol and dipropylene glycol.
Compared with the prior art, the invention has the advantages that:
the vinyl resin of the invention is prepared by chain extending epoxy resin with dibasic acid to make two ends of the vinyl resin carry carboxyl, and grafting unsaturated double bond on the side chain of the vinyl resin, thereby improving the crosslinkability of the vinyl resin and the compatibility with an active diluent. In addition, because the vinyl resin of the invention has terminal carboxyl, when alkaline earth metal oxide (such as magnesium oxide, calcium oxide and the like) is further added after the carboxyl-terminated unsaturated polyester is added on the basis, the terminal carboxyl reacts with the alkaline earth metal oxide to further extend the chain of the vinyl resin and increase the molecular weight, thereby achieving remarkable thickening effect, namely, the vinyl composition consisting of the vinyl resin, the reactive diluent and the unsaturated polyester has remarkable thickening effect.
Drawings
FIG. 1 is an IR spectrum of a vinyl resin in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1
(1) Synthesis of TDI-HPMA
330g of styrene, 0.045g of methyl hydroquinone and 147.7g of toluene-diisocyanate are added, the temperature is slowly raised to 80 ℃, 122.3g of hydroxypropyl methacrylate is added dropwise within 30min, the temperature is kept for 2h, 300g of styrene is added when the NCO content is detected to be 5.94% of the theoretical value, and the reaction is stopped by cooling, thus obtaining the TDI-HPMA solution with the NCO content of 3.96%.
(2) Preparation of vinyl resins
419g of basic epoxy 828 (EEW = 189), 58.7g of bisphenol A and 0.25g of tetramethylammonium chloride are added, stirring is started, the mixture is heated to 145 ℃ and reacted for 2 hours at constant temperature, the temperature is reduced to 80 ℃, 0.21g of methyl hydroquinone, 41g of fumaric acid, 1g of benzyltriethylammonium chloride and 91.4g of methacrylic acid are added, the temperature is increased to 120 ℃ and 125 ℃, the mixture is reacted to the acid value of 30-35, the temperature is reduced to 80 ℃, 242g of TDI-HPMA solution obtained in the step (1) is added, the reaction is carried out for 2 hours at constant temperature, 287g of styrene is added, the mixture is cooled and discharged, the solid content of the obtained resin is 60 percent, and the viscosity is 1.8 Pa.s.
The infrared spectrum of the vinyl resin is shown in figure 1:
CH3,CH2the absorption band of CH and the absorption band of CH are located at 3200-2850 cm-1；1700cm-1Characteristic absorption peak of C = O; 1600cm-1Is the C = C characteristic absorption peak on the methacrylic acid backbone; 1500cm-1C = C characteristic absorption peak on benzene ring; 1250cm-1Is a C-O-C absorption peak on a benzene ring; 1100cm-1Is the C-C absorption peak on the benzene ring.
Example 2
Synthesis of carboxyl-terminated unsaturated polyester
Adding 476g of adipic acid, 38g of maleic anhydride and 368g of neopentyl glycol, slowly heating to 150 ℃, reacting at constant temperature for 1h, then heating to 200 ℃ at a heating rate of 10 ℃/h, reacting at 200 ℃ in a heat preservation manner, starting vacuum dehydration until the acid value reaches a target value of 16-20 and the corresponding number average molecular weight is 5600 when the acid value does not significantly decrease.
Comparative example 1
Preparation of vinyl resin: 409g of basic epoxy 828 (EEW = 189), 88.3g of bisphenol A and 0.25g of tetramethylammonium chloride are added, stirring is started, the mixture is heated to 145 ℃ for constant-temperature reaction for 2 hours, the temperature is reduced to 80 ℃, 0.21g of methyl hydroquinone, 1g of benzyl triethyl ammonium chloride and 120.4g of methacrylic acid are added, the temperature is increased to 110 ℃, when the acid value is 6-8 after the reaction, 6g of maleic anhydride is added, the reaction is carried out for 15 minutes, 372g of styrene is added, cooling and discharging are carried out, the solid content of the obtained resin is 62%, and the viscosity is 0.56Pa.s (25 ℃).
The vinyl resin of example 1 and comparative example 1 was prepared according to the following table for the thickening test, magnesium oxide was added, and the viscosity was measured immediately after stirring uniformly; after that, the mixture was left at 45 ℃ for 24 hours, cooled to 25 ℃ and immediately tested for viscosity, and the thickening effect was evaluated.
In addition to the above embodiments, the present invention also includes other embodiments, and any technical solutions formed by equivalent transformation or equivalent replacement should fall within the scope of the claims of the present invention.
Claims (10)
1. An ethylene-based resin characterized by: the structural formula is as follows:
2. a preparation method of vinyl resin is characterized in that: the method comprises the following steps:
(1) reacting dibasic acid with epoxy resin to prepare carboxyl-terminated polyepoxy polymer, wherein the epoxy resin is basic epoxy or bisphenol A epoxy resin prepared by chain extension of the basic epoxy by bisphenol A;
(2) and (2) reacting the carboxyl-terminated epoxy polymer prepared in the step (1) with polyurethane to prepare the vinyl resin.
3. The method for producing an ethylene-based resin according to claim 2, characterized in that: in the step (1), the carboxyl-terminated polyepoxy polymer is prepared by using dibasic acid and epoxy resin in the presence of a unit acid containing a carbon-carbon double bond.
4. The method for producing an ethylene-based resin according to claim 3, characterized in that: the unit acid containing carbon-carbon double bonds is one or more of acrylic acid, methacrylic acid, 2-butenoic acid and cinnamic acid.
5. The method for producing an ethylene-based resin according to claim 2, characterized in that: in the step (1), the dibasic acid is one or more of adipic acid, succinic acid, fumaric acid and succinic acid.
6. The method for producing an ethylene-based resin according to claim 2, characterized in that: in the step (1), the epoxy resin is a compound represented by the following formula (1) or formula (2):
7. the method for producing an ethylene-based resin according to claim 2, characterized in that: the polyurethane in the step (2) is a polymer of diisocyanate and hydroxy (methyl) acrylate; the diisocyanate is one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene-2, 4-diisocyanate (2, 4-TDI), toluene-2, 6-diisocyanate (2, 6-TDI), 4 '-diphenylmethane diisocyanate (MDI) and hydrogenated 4, 4' -diphenylmethane diisocyanate (H12 MDI); the hydroxyl (methyl) acrylate is one or more of hydroxyethyl (methyl) acrylate and hydroxypropyl (methyl) acrylate.
8. A thickened vinyl resin composition characterized by: comprising the vinyl resin, the reactive diluent, and the carboxyl-terminated unsaturated polyester according to claim 1.
9. The thickened vinyl resin composition according to claim 8, characterized in that: the active diluent is one or more of styrene, vinyl toluene, divinylbenzene and acrylate.
10. The thickened vinyl resin composition according to claim 8, characterized in that: the carboxyl-terminated unsaturated polyester has the number average molecular weight of more than 4000 and is formed by polymerizing dibasic acid, dibasic anhydride and dihydric alcohol; the dibasic acid is one or more of adipic acid, succinic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid and maleic acid; the dibasic acid anhydride is one or more of succinic anhydride, phthalic anhydride and maleic anhydride; the dihydric alcohol is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, butanediol, neopentyl glycol, 2-methyl-1, 3-propylene glycol, diethylene glycol and dipropylene glycol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416281A (en) * | 2021-07-05 | 2021-09-21 | 常州天马集团有限公司（原建材二五三厂） | Unsaturated polyester resin for sheet molding compound and preparation method thereof |
Citations (7)
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|---|---|---|---|---|
| WO1979000240A1 (en) * | 1977-10-28 | 1979-05-03 | Dainippon Ink & Chemicals | Modified copolymers and process for production thereof |
| CN1687191A (en) * | 2005-04-01 | 2005-10-26 | 合肥工业大学 | Aqucous polyurethane modified from vinyl resin possessing structure of bisphenol A and its preparing process |
| US20150119497A1 (en) * | 2012-03-29 | 2015-04-30 | Sanyo Chemical Industries, Ltd. | Vinyl resin and resin composition |
| CN111440266A (en) * | 2020-04-24 | 2020-07-24 | 南京聚发新材料有限公司 | Reactive flame retardant, unsaturated resin containing the same, and method for preparing the same |
| CN111499801A (en) * | 2020-04-24 | 2020-08-07 | 南京聚发新材料有限公司 | Reactive type flame retardant capable of thickening, flame retardant vinyl SMC resin containing same and method for preparing same |
| CN111499806A (en) * | 2020-04-24 | 2020-08-07 | 南京聚发新材料有限公司 | Unsaturated resin or vinyl resin composition and application thereof in composite material |
| CN111995755A (en) * | 2020-08-24 | 2020-11-27 | 浙江晨诺高分子材料有限公司 | Vinyl ester flame-retardant resin containing polyester structure and preparation method thereof |
-
2021
- 2021-02-26 CN CN202110216776.7A patent/CN112940263B/en active Active
Patent Citations (7)
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| WO1979000240A1 (en) * | 1977-10-28 | 1979-05-03 | Dainippon Ink & Chemicals | Modified copolymers and process for production thereof |
| CN1687191A (en) * | 2005-04-01 | 2005-10-26 | 合肥工业大学 | Aqucous polyurethane modified from vinyl resin possessing structure of bisphenol A and its preparing process |
| US20150119497A1 (en) * | 2012-03-29 | 2015-04-30 | Sanyo Chemical Industries, Ltd. | Vinyl resin and resin composition |
| CN111440266A (en) * | 2020-04-24 | 2020-07-24 | 南京聚发新材料有限公司 | Reactive flame retardant, unsaturated resin containing the same, and method for preparing the same |
| CN111499801A (en) * | 2020-04-24 | 2020-08-07 | 南京聚发新材料有限公司 | Reactive type flame retardant capable of thickening, flame retardant vinyl SMC resin containing same and method for preparing same |
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| CN111995755A (en) * | 2020-08-24 | 2020-11-27 | 浙江晨诺高分子材料有限公司 | Vinyl ester flame-retardant resin containing polyester structure and preparation method thereof |
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| Title |
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| FAN, LH等: "Thermal analysis during the formation of polyurethane and vinyl ester resin interpenetrating polymer networks", 《POLYMER》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416281A (en) * | 2021-07-05 | 2021-09-21 | 常州天马集团有限公司（原建材二五三厂） | Unsaturated polyester resin for sheet molding compound and preparation method thereof |
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Effective date of registration: 20211229 Address after: 214021 No. 888, Jiefang East Road, Nanchang District, Wuxi City, Jiangsu Province Applicant after: Li Shibing Address before: 226400 308, yangkougang business building, 1 Bohai Road, Changsha Town, Rudong County, Nantong City, Jiangsu Province Applicant before: Meigao microsphere (Nantong) Technology Co.,Ltd. |
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