CN111349222A - Flexible unsaturated polyester resin and preparation method thereof - Google Patents
Flexible unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN111349222A CN111349222A CN202010336581.1A CN202010336581A CN111349222A CN 111349222 A CN111349222 A CN 111349222A CN 202010336581 A CN202010336581 A CN 202010336581A CN 111349222 A CN111349222 A CN 111349222A
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- polyester resin
- unsaturated polyester
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- diacid
- flexible unsaturated
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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
- 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
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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
- 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
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a flexible unsaturated polyester resin and a preparation method thereof, wherein the flexible unsaturated polyester resin is prepared by carrying out polycondensation reaction on dihydric alcohol, aliphatic diacid or aliphatic diacid anhydride, aromatic diacid or aromatic diacid anhydride and lactone, and then diluting the unsaturated active monomer, and hydroquinone is used as a polymerization inhibitor for preventing gel from appearing in the polymerization process. The flexible unsaturated polyester resin disclosed by the invention has excellent flexibility and impact strength, and meets the physical property requirements of button products.
Description
Technical Field
The invention belongs to the technical field of unsaturated polyester resin, and particularly relates to flexible unsaturated polyester resin and a preparation method thereof.
Background
The button is generally prepared by using Unsaturated Polyester Resin (UPR) as a main raw material, adding a proper amount of additives, carrying out gelation and solidification in specific equipment and a mold to obtain a pearlized or non-pearlized plate, and carrying out machining.
The unsaturated polyester resin which is the main raw material for preparing the button is a linear high molecular compound with multifunctional groups, a backbone of the unsaturated polyester resin is provided with a polyester chain bond and an unsaturated double bond, and two ends of the high molecular chain are respectively provided with a carboxyl group and a hydroxyl group, and the unsaturated polyester resin is usually prepared by polycondensation of dibasic acid or corresponding anhydride and dihydric alcohol. The common unsaturated resin is generally prepared by polycondensation of phthalic anhydride, maleic anhydride, ethylene glycol, propylene glycol and diethylene glycol, and is a high molecular compound with ester bonds and unsaturated double bonds.
In order to improve the toughness of the unsaturated polyester resin, some dibasic acids having flexible bonds, such as adipic acid, succinic acid (anhydride), etc., or some glycols having flexible bonds, such as diethylene glycol, dipropylene glycol, etc., are generally added, but the tensile strength, flexural strength, and hardness are significantly reduced while the flexibility and impact strength are improved.
Chinese patent CN 107602829a discloses a flexible unsaturated polyester resin, which is prepared by condensation polymerization of polyhydric alcohol, maleic anhydride and dibasic acid to obtain unsaturated polyester, hydroquinone is used as polymerization inhibitor to prevent gelation during polymerization, and then flexible dibasic acid is combined, the long flexible aliphatic chain structure in the flexible dibasic acid has excellent flexibility, elasticity and high extensibility, so that the unsaturated polyester resin has excellent flexibility, but other mechanical properties of the unsaturated resin, such as tensile property and hardness, can be greatly reduced.
Disclosure of Invention
The invention aims to provide a flexible unsaturated polyester resin and a preparation method thereof, and the prepared flexible unsaturated polyester resin has excellent flexibility and impact strength and avoids the defect that other mechanical properties are reduced.
The technical scheme adopted by the invention for solving the problems is as follows: a flexible unsaturated polyester resin having the structural formula I:
formula I
Wherein Ap is a divalent organic group of an aliphatic diacid or an aliphatic dianhydride, G1 and G2 are divalent organic groups of a diol, Ar is a divalent organic group of an aromatic diacid or an aromatic dianhydride, Cp is a divalent group of a lactone, and a, b, c and d represent the number of repeating structural units.
The general structural formula of the lactone is shown as formula II:
formula II
Wherein n =3~ 7.
Preferably, the fatty diacid or fatty diacid anhydride is at least one of adipic acid, succinic anhydride, fumaric acid, maleic acid and maleic anhydride.
Preferably, the aromatic diacid or aromatic diacid anhydride is at least one of phthalic acid, phthalic anhydride, isophthalic acid and terephthalic acid.
Preferably, the dihydric alcohol is at least one 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.
Another object of the present invention is to provide a method for preparing a flexible unsaturated polyester resin, comprising the steps of:
adding dihydric alcohol, fatty diacid or fatty diacid anhydride, aromatic diacid or aromatic diacid anhydride and lactone into a reaction kettle, preserving heat for 30min under the protection of nitrogen, heating to 210 ℃ at the speed of 5 ℃/10min, cooling to 120 ℃ after the acid value reaches 18-21mgKOH/g and the viscosity of a vertebral plate is 6.5-8.0P (150 ℃), adding hydroquinone, stirring uniformly, and adding an unsaturated reactive monomer for dilution to obtain the flexible unsaturated polyester resin.
Preferably, the unsaturated reactive monomer is at least one of styrene, vinyl toluene, divinylbenzene and acrylate.
Preferably, the mass percentages of the dihydric alcohol, the aliphatic diacid or aliphatic diacid anhydride, the aromatic diacid or aromatic diacid anhydride and the lactone are respectively 10-40%, 20-40%, 25-40% and 5-15%.
Preferably, the hydroquinone is added in an amount of 0.005-0.02% of the mass of the unsaturated polyester resin reactant.
Preferably, the amount of the unsaturated reactive monomer added is 30-45% of the mass of the unsaturated polyester resin reaction product.
Compared with the prior art, the invention has the advantages that:
according to the invention, the lactone monomer is added into the unsaturated polyester resin raw material, the lactone structural unit is introduced, and the ester bond structure in the unsaturated polyester is reduced, so that the prepared unsaturated polyester resin has more excellent flexibility and impact strength, does not influence other mechanical properties, and meets the physical property requirements of button products.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Adding 530.57g of diethylene glycol, 245.18g of adipic acid, 520.19g of isophthalic acid, 276.69g of maleic anhydride, 104.77g of propylene glycol, 62.57g of neopentyl glycol and 91.57g of caprolactone into a 3.0L reaction kettle, introducing nitrogen, slowly heating to a distillation head at the speed of 5 ℃/10min to discharge water, recording the temperature of the reaction kettle, keeping the temperature for 30min, slowly and uniformly heating to 210 ℃ at the speed of 5 ℃/10min until the acid value reaches 18-21mgKOH/g and the vertebral plate viscosity is 6.5-8.0P (150 ℃), cooling to 120 ℃, adding 0.1739g of hydroquinone, uniformly stirring, and adding 787.64g of styrene for dilution to obtain the flexible unsaturated polyester resin.
Example 2
Adding 530.57g of diethylene glycol, 245.18g of adipic acid, 520.19g of isophthalic acid, 276.69g of maleic anhydride, 104.77g of propylene glycol, 62.57g of neopentyl glycol and 193.33g of caprolactone into a 3.0L reaction kettle, introducing nitrogen, slowly heating to a distillation head at the speed of 5 ℃/10min to discharge water, recording the temperature of the reaction kettle, keeping the temperature for 30min, slowly and uniformly heating to 210 ℃ at the speed of 5 ℃/10min until the acid value reaches 18-21mgKOH/g and the vertebral plate viscosity is 6.5-8.0P (150 ℃), cooling to 120 ℃, adding 0.1739g of hydroquinone, uniformly stirring, and adding 787.64g of styrene for dilution to obtain the flexible unsaturated polyester resin.
Comparative example
Adding 530.57g of diethylene glycol, 245.18g of adipic acid, 520.19g of isophthalic acid, 276.69g of maleic anhydride, 104.77g of propylene glycol and 62.57g of neopentyl glycol into a 3.0L reaction kettle, introducing nitrogen, slowly heating to a distillation head at the speed of 5 ℃/10min until water flows out, recording the temperature of the reaction kettle, keeping the temperature for 30min, slowly and uniformly heating to 210 ℃ at the speed of 5 ℃/10min until the acid value reaches 18-21mgKOH/g and the vertebral plate viscosity is 6.5-8.0P (150 ℃), cooling to 120 ℃, adding 0.1739g of hydroquinone, uniformly stirring, adding 787.64g of styrene for dilution, and thus obtaining the flexible unsaturated polyester resin.
The unsaturated polyester resin styrene solutions obtained in example 1, example 2 and comparative example were formed into sheets and then subjected to a performance test, and the obtained data are shown in table 1:
the specific preparation process of the sheet comprises the following steps: the styrene solutions of unsaturated polyester resins obtained in examples and comparative examples were mixed with 4% cobalt octoate/styrene solution (cobalt content: 1%) and 2% methyl ethyl ketone peroxide (content: 50%) based on the weight of the liquid resin, mixed and defoamed, poured into a mold, allowed to stand at room temperature for 12 hours for preforming, aged at 80 ℃ for 2 hours, further aged at 100 ℃ for 2 hours, and cut into test pieces according to the test standards for various mechanical tests.
Table 1 table of performance test results
As can be seen from the table above, compared with the comparative example, the unsaturated polyester resin prepared by adding the lactone in the invention has more excellent flexibility and impact strength on the basis of not influencing other mechanical properties.
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 (9)
1. A flexible unsaturated polyester resin characterized by: the structural formula of the flexible unsaturated polyester resin is shown as formula I:
formula I
Wherein Ap is a divalent organic group of an aliphatic diacid or an aliphatic dianhydride, G1 and G2 are divalent organic groups of a diol, Ar is a divalent organic group of an aromatic diacid or an aromatic dianhydride, Cp is a divalent group of a lactone, and a, b, c and d represent the number of repeating structural units; the general structural formula of the lactone is shown as formula II:
formula II
Wherein n =3~ 7.
2. The flexible unsaturated polyester resin according to claim 1, wherein: the fatty diacid or fatty dianhydride is at least one of adipic acid, succinic anhydride, fumaric acid, maleic acid and maleic anhydride.
3. The flexible unsaturated polyester resin according to claim 1, wherein: the aromatic diacid or aromatic dianhydride is at least one of phthalic acid, phthalic anhydride, isophthalic acid and terephthalic acid.
4. The flexible unsaturated polyester resin according to claim 1, wherein: the dihydric alcohol is at least one 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.
5. A process for preparing a flexible unsaturated polyester resin according to any of claims 1 to 4, characterized in that: the method comprises the following steps: adding dihydric alcohol, fatty diacid or fatty diacid anhydride, aromatic diacid or aromatic diacid anhydride and lactone into a reaction kettle, preserving heat for 30min under the protection of nitrogen, heating to 210 ℃ at the speed of 5 ℃/10min, cooling to 120 ℃ after the acid value reaches 18-21mgKOH/g, adding hydroquinone, stirring uniformly, and adding an unsaturated active monomer for dilution to obtain the flexible unsaturated polyester resin.
6. The method for preparing a flexible unsaturated polyester resin according to claim 5, wherein: the unsaturated active monomer is at least one of styrene, vinyl toluene, divinyl benzene and acrylate.
7. The method for preparing a flexible unsaturated polyester resin according to claim 5, wherein: the mass percentages of the dihydric alcohol, the aliphatic diacid or aliphatic dianhydride, the aromatic diacid or aromatic dianhydride and the lactone are respectively 10-40%, 20-40%, 25-40% and 5-15%.
8. The method for preparing a flexible unsaturated polyester resin according to claim 5, wherein: the addition amount of the hydroquinone is 0.005-0.02% of the mass of the unsaturated polyester resin reactant.
9. The method for preparing a flexible unsaturated polyester resin according to claim 5, wherein: the addition amount of the unsaturated active monomer is 30-45% of the mass of the unsaturated polyester resin reactant.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010336581.1A CN111349222A (en) | 2020-04-26 | 2020-04-26 | Flexible unsaturated polyester resin and preparation method thereof |
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| CN202010336581.1A CN111349222A (en) | 2020-04-26 | 2020-04-26 | Flexible unsaturated polyester resin and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090312485A1 (en) * | 2008-06-11 | 2009-12-17 | E. I. Dupont De Nemours And Company | Unsaturated polyester resin compositions comprising 1,3-propanediol |
| CN106905909A (en) * | 2017-03-20 | 2017-06-30 | 苏州瀚海新材料有限公司 | In-situ polymerization curing polyester adhesive based on lactone and preparation method thereof |
| CN107446472A (en) * | 2017-08-04 | 2017-12-08 | 合众（佛山）化工有限公司 | A kind of waterborne polyester coating modified unsaturated polyester emulsion and preparation method thereof |
| CN109952336A (en) * | 2017-05-03 | 2019-06-28 | 阿克伦大学 | The block copolymer of lactone and poly- (fumaric acid propylene glycol ester) |
-
2020
- 2020-04-26 CN CN202010336581.1A patent/CN111349222A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090312485A1 (en) * | 2008-06-11 | 2009-12-17 | E. I. Dupont De Nemours And Company | Unsaturated polyester resin compositions comprising 1,3-propanediol |
| CN106905909A (en) * | 2017-03-20 | 2017-06-30 | 苏州瀚海新材料有限公司 | In-situ polymerization curing polyester adhesive based on lactone and preparation method thereof |
| CN109952336A (en) * | 2017-05-03 | 2019-06-28 | 阿克伦大学 | The block copolymer of lactone and poly- (fumaric acid propylene glycol ester) |
| CN107446472A (en) * | 2017-08-04 | 2017-12-08 | 合众（佛山）化工有限公司 | A kind of waterborne polyester coating modified unsaturated polyester emulsion and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| M. MESSORI. ET AL.: "Unsaturated polyester resins modified with poly(ε-caprolactone)–perfluoropolyethers block copolymers", 《POLYMER》 * |
| 余桐柏等: "不饱和PDMS-PCL嵌段共聚物的合成及其在不饱和聚酯树脂中的应用", 《广东化工》 * |
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