CN111892702B - Terephthalic acid type unsaturated polyester resin and preparation method thereof - Google Patents
Terephthalic acid type unsaturated polyester resin and preparation method thereof Download PDFInfo
- Publication number
- CN111892702B CN111892702B CN202010759554.5A CN202010759554A CN111892702B CN 111892702 B CN111892702 B CN 111892702B CN 202010759554 A CN202010759554 A CN 202010759554A CN 111892702 B CN111892702 B CN 111892702B
- Authority
- CN
- China
- Prior art keywords
- temperature
- percent
- terephthalic acid
- polyester resin
- unsaturated polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
Landscapes
- 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 terephthalic acid type unsaturated polyester resin, which is synthesized by a three-step process, wherein a reaction system comprises the following components in percentage by weight: the first step, terephthalic acid 14-20%, methyl propylene glycol 18-23%, trimethylolpropane 3-4%, catalyst 0.02%; step two, 33 to 40 percent of maleic anhydride, 19 to 21 percent of dihydric alcohol and 0.06 to 0.07 percent of antioxidant; thirdly, maleic anhydride 3 percent and polymerization inhibitor 0.02-0.03 percent. The invention adopts a three-step process to synthesize the terephthalic acid type SMC/BMC unsaturated polyester resin, does not need a pressurization process, adopts terephthalic acid as the saturated dibasic acid, does not use other saturated dibasic acids except terephthalic acid, and can synthesize the polyester resin with good compatibility with styrene, good resin transparency and good physical and mechanical properties. The resin is used for SMC/BMC products, and can improve the performances such as heat resistance, mechanical strength and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to terephthalic acid type unsaturated polyester resin and a preparation method thereof.
Background
The unsaturated polyester resin is widely applied to industries such as industry, agriculture, national defense and building, especially SMC, BMC and other mold pressure reinforced unsaturated polyesters, and has the advantages of high strength and stable part size, so the unsaturated polyester resin is developed quickly. At present, the consumption of polyester in the polyester glass fiber reinforced plastics accounts for 70 to 80 percent of the total consumption of polyester. At present, unsaturated polyester resin commonly used in chemical enterprises for SMC/BMC matrix resin is mainly o-benzene unsaturated polyester, p-benzene unsaturated polyester resin is used as matrix resin, the wetting property with glass fiber is good, and the heat resistance, water resistance and chemical resistance are improved, so that the p-benzene unsaturated polyester resin is proposed to be applied to SMC/BMC.
The p-benzene type unsaturated polyester resin is a new product developed successfully in recent years. The terephthalic acid with a linear structure replaces phthalic acid, carboxyl of the terephthalic acid is positioned on para-position of a benzene ring, the interaction is small, and the chemical property is stable, so that the polyester resin has good chemical corrosion resistance, and meanwhile, the polyester macromolecular structure is symmetrical and is arranged in order, so that the polyester resin has good electrical property, mechanical property and heat resistance. The chemical resistance and the heat resistance of the polyester resin are particularly outstanding, which are superior to the m-benzene unsaturated polyester resin and are more incomparable with the o-benzene unsaturated polyester resin, and the price of the polyester resin is lower than that of the m-benzene unsaturated polyester resin and is equivalent to that of the o-benzene unsaturated polyester resin.
However, in the process of synthesizing the p-benzene unsaturated polyester resin, the carboxyl of terephthalic acid is positioned at the para position of a benzene ring, the interaction is small, the chemical property is stable, the reaction activity with dihydric alcohol is poor, strong acid is needed as a catalyst, high temperature and pressure are needed for reaction, the reaction time is long, the compatibility of the synthesized polyester and styrene is poor, and the synthetic polyester is easy to delaminate, so that the use value is lost. In the process of synthesizing the p-benzene unsaturated resin, a two-step method is generally used, pressure synthesis is required, the process has difficulty for many resin factories, the equipment requirement is high, and the alcohol synthesized in the first step has too low boiling point, and if the alcohol is not pressurized, the alcohol is difficult to completely react with terephthalic acid.
Disclosure of Invention
The invention aims to solve the technical problems and provide a terephthalic acid type unsaturated polyester resin which has good compatibility with styrene, good resin transparency and good mechanical and physical properties.
In order to realize the aim, the invention provides terephthalic acid type unsaturated polyester resin which is synthesized by a three-step normal pressure process, wherein a reaction system comprises the following components in percentage by weight: the first step, terephthalic acid 14-20%, methyl propylene glycol 18-23%, trimethylolpropane 3-4%, catalyst 0.02%; step two, 33 to 40 percent of maleic anhydride, 19 to 21 percent of dihydric alcohol and 0.06 to 0.07 percent of antioxidant; thirdly, 3 percent of maleic anhydride and 0.02 to 0.03 percent of polymerization inhibitor.
Preferably, the terephthalic-type unsaturated polyester resin of the present invention further comprises styrene in an amount of 30 to 40% based on the sum of styrene and the weight of the reaction system. More preferably, the styrene content is from 30% to 31%. Preferably, it also contains 0.01% by weight of copper isooctanoate.
Preferably, the catalyst is monobutyltin oxide.
Preferably, the antioxidant is triphenyl phosphite.
Preferably, the polymerization inhibitor is methyl hydroquinone.
Preferably, the glycol is ethylene glycol or propylene glycol or a mixture of both.
On the other hand, the invention also provides a preparation method of the terephthalic acid type unsaturated polyester resin, which comprises the following steps:
step 1: adding the wet material and the auxiliary agent in the first step, stirring uniformly, adding the dry material under stirring, after the feeding is finished, supplying nitrogen, heating, controlling the distillation temperature to be not more than 103 ℃, controlling the highest material temperature to be not more than 215 ℃, stopping heating and cooling when the sampled material is transparent and the acid value is less than 5 mgKOH/g;
and 2, step: when the temperature of the material is reduced to 180 ℃, adding the wet material and the auxiliary agent in the second step, adding the dry material, heating after the material is added, controlling the distillation temperature to be not more than 102 ℃, controlling the highest temperature of the material to be not more than 205 ℃, increasing the nitrogen amount when the distillation temperature is lower than 90 ℃, reacting at the constant temperature of 205 ℃, controlling the viscosity of the polyester as the end point when the constant temperature reaction is carried out until the acid value is less than 15mgKOH/g and the viscosity of the polyester is 40-42P/120 ℃, and starting to reduce the temperature;
and 3, step 3: when the temperature of the materials is reduced to 180 ℃, adding the polymerization inhibitor and the dry materials in the third step, keeping the temperature at 175-180 ℃ for 1 hour, then reducing the temperature, and diluting with styrene.
Preferably, when the dilution is carried out in the step 3, the dilution temperature does not exceed 85 ℃.
The invention adopts a three-step process to synthesize the terephthalic acid type SMC/BMC unsaturated polyester resin, does not need a pressurization process, adopts terephthalic acid as the saturated dibasic acid, does not use other saturated dibasic acids except terephthalic acid, and can synthesize the polyester resin with good styrene compatibility and good resin transparency. The resin is used for SMC/BMC products, and can improve the performances such as heat resistance, water resistance and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the instruments or reagents used in the examples are conventional reagents or instruments in the art, and are conventional products available on the market. Unless otherwise stated, the specific experimental procedures mentioned herein are understood or known by those skilled in the art based on common general knowledge or conventional technical means, and are not described in detail. For the sake of brevity, the parameters of the procedures, steps and equipment used are not described in detail in part of the procedures, it being understood that these are well known to those skilled in the art and are reproducible.
Example 1
The formula of the reaction kettle is as follows: in the first step, 200g of purified terephthalic acid, 290g of methyl propanediol, 55g of trimethylolpropane and 0.3g of catalyst monobutyl tin oxide; step two, 560g of maleic anhydride, 300g of propylene glycol and 1g of antioxidant triphenyl phosphite; in the third step, 50g of maleic anhydride and 0.4g of polymerization inhibitor methyl hydroquinone are added.
The formula of the dilution kettle is as follows: 650g of styrene and 0.2g of copper isooctanoate.
The preparation process comprises the following steps: and (5) checking whether the equipment, the electric appliance, the instrument, the valve and the A-grade raw material are normal or not. Adding the first-step wet material (methyl propylene glycol) and the catalyst into a reaction pot according to the formula, stirring uniformly, and adding the dry material (refined terephthalic acid and trimethylolpropane) into the reaction pot under stirring. After feeding, nitrogen (2 cubic meters per hour) is supplied to the reaction kettle, water is supplied to the horizontal condenser, the temperature is rapidly raised, the distillation temperature is controlled to be not more than 103 ℃, and the highest material temperature is not more than 215 ℃. When the sampled material is transparent and the acid value is less than 5mgKOH/g, the reaction kettle stops heating and cooling. When the temperature of the material is reduced to 180 ℃, adding the wet material (propylene glycol) and the antioxidant in the second step, and then adding the dry material (maleic anhydride); after the feeding is finished, the temperature is quickly raised, the distillation temperature is controlled to be not more than 102 ℃, the highest temperature of the material is not more than 205 ℃, when the distillation temperature is lower than 90 ℃, the nitrogen amount is increased to 10 cubic meters per hour, and the reaction is carried out at the constant temperature of 205 ℃. And (3) carrying out constant temperature reaction until the acid value is less than 15mgKOH/g and the viscosity of the polyester is 40-42P/120 ℃, and cooling the reaction kettle by taking the viscosity of the polyester as an end point. When the temperature of the materials is reduced to 180 ℃, adding an auxiliary material polymerization inhibitor, adding the third step dry material (maleic anhydride), keeping the temperature at 180 ℃ for 1 hour, then reducing the temperature, and immediately starting to dilute in a pot (styrene and copper isooctanoate are added into a diluting pot in advance).
The dilution temperature is controlled below 85 ℃.
Example 2
The formula of the reaction kettle is as follows: in the first step, 250g of purified terephthalic acid, 310g of methyl propanediol, 60g of trimethylolpropane and 0.3g of catalyst monobutyl tin oxide; step two, 660g of maleic anhydride, 124 g of ethylene glycol, 217g of propylene glycol and 1g of antioxidant triphenyl phosphite; step three, 55g of maleic anhydride and 0.4g of polymerization inhibitor methyl hydroquinone.
The formula of the dilution kettle is as follows: 750g of styrene and 0.25g of copper isooctanoate.
The preparation process comprises the following steps: and (4) checking whether the equipment, the electric appliance, the instrument, the valve and the A-grade raw material are normal or not. According to the formula, the first-step wet material (methyl propanediol) and the catalyst are respectively put into a reaction pot, and after being uniformly stirred, the dry material (refined terephthalic acid and trimethylolpropane) is put into the reaction pot under stirring. After the feeding is finished, nitrogen (the nitrogen amount is 2 cubic meters per hour) is supplied to the reaction kettle, water is supplied to the horizontal condenser, the temperature is rapidly raised, the distillation temperature is controlled to be not more than 103 ℃, and the highest material temperature is not more than 215 ℃. When the sampled material is transparent and the acid value is less than 5mgKOH/g, the reaction kettle stops heating and cooling. When the temperature of the materials is reduced to 180 ℃, the wet materials (ethylene glycol and propylene glycol) and the antioxidant in the second step are added, and then the dry materials (maleic anhydride) are added; after the feeding is finished, the temperature is quickly raised, the distillation temperature is controlled to be not more than 102 ℃, the highest temperature of the material is not more than 205 ℃, when the distillation temperature is lower than 90 ℃, the nitrogen content is increased to 10 cubic meters per hour, and the reaction is carried out at the constant temperature of 205 ℃. And (3) carrying out constant temperature reaction until the acid value is less than 15mgKOH/g and the viscosity of the polyester is 38-41P/120 ℃, and cooling the reaction kettle by taking the viscosity of the polyester as an end point. When the temperature of the materials is reduced to 180 ℃, adding an auxiliary material polymerization inhibitor, adding the maleic anhydride in the third step, keeping the temperature at 175 ℃ for 1 hour, then reducing the temperature, and immediately starting to dilute in a pot (styrene and copper isooctanoate are added into a diluting pot in advance).
The dilution temperature is controlled below 85 ℃.
Example 3
The formula of the reaction kettle is as follows: 300g of purified terephthalic acid, 350g of methyl propylene glycol, 50g of trimethylolpropane and 0.35g of catalyst monobutyl tin oxide; step two, 520g of maleic anhydride, 295g of propylene glycol and 1g of antioxidant triphenyl phosphite; step three, 40g of maleic anhydride and 0.3g of polymerization inhibitor methyl hydroquinone.
The formula of the dilution kettle is as follows: 700g of styrene and 0.25g of copper isooctanoate.
The preparation process comprises the following steps: and (4) checking whether the equipment, the electric appliance, the instrument, the valve and the A-grade raw material are normal or not. According to the formula of the reaction kettle, the first-step wet material (methyl propylene glycol) and the catalyst are respectively put into the reaction kettle, and after the first-step wet material and the catalyst are uniformly stirred, the dry materials (refined terephthalic acid and trimethylolpropane) are put into the reaction kettle under the stirring. After the feeding is finished, nitrogen (the nitrogen amount is 2 cubic meters per hour) is supplied to the reaction kettle, water is supplied to the horizontal condenser, the temperature is rapidly raised, the distillation temperature is controlled to be not more than 103 ℃, and the highest material temperature is not more than 215 ℃. When the sampled material is transparent and the acid value is less than 5mgKOH/g, the reaction kettle stops heating and cooling. When the temperature of the material is reduced to 180 ℃, adding the wet material (propylene glycol) and the antioxidant in the second step, and then adding the dry material (maleic anhydride); after the feeding is finished, the temperature is quickly raised, the distillation temperature is controlled to be not more than 102 ℃, the highest temperature of the material is not more than 205 ℃, when the distillation temperature is lower than 90 ℃, the nitrogen content is increased to 10 cubic meters per hour, and the reaction is carried out at the constant temperature of 205 ℃. Reacting at constant temperature until the acid value is less than 15mgKOH/g and the polyester viscosity is 42-48P/120 ℃, and cooling the reaction kettle by taking the polyester viscosity as a terminal point. When the temperature of the materials is reduced to 180 ℃, adding an auxiliary material polymerization inhibitor, adding the maleic anhydride in the third step, keeping the temperature at 180 ℃ for 1 hour, then cooling, and immediately beginning to put into a pot for dilution (styrene and copper isooctanoate are added into a dilution pot in advance).
The dilution temperature is controlled below 85 ℃.
Comparative example
The formula of the reaction kettle is as follows: in the first step, 320g of purified terephthalic acid, 375g of methyl propanediol, 50g of trimethylolpropane and 0.35g of catalyst are added; 560g of maleic anhydride, 295g of propylene glycol and 1g of antioxidant; 0.3g of polymerization inhibitor.
The formula of the dilution kettle is as follows: 700g of styrene and 0.25g of copper isooctanoate.
The preparation process comprises the following steps: and (4) checking whether the equipment, the electric appliance, the instrument, the valve and the A-grade raw material are normal or not. Respectively adding the first-step wet material (methyl propylene glycol) and the catalyst into a reaction kettle according to the formula of the reaction kettle, uniformly stirring, and then adding the dry materials (refined terephthalic acid and trimethylolpropane) into the reaction kettle under stirring. After feeding, nitrogen (the nitrogen amount is 2 cubic meters per hour) is supplied to the reaction kettle, water is supplied to the horizontal condenser, the temperature is rapidly raised, the distillation temperature is controlled to be not more than 103 ℃, and the highest material temperature is not more than 215 ℃. When the sampled material is transparent and the acid value is less than 5mgKOH/g, the reaction kettle stops heating and cooling. When the temperature of the material is reduced to 180 ℃, the wet material (propylene glycol) and the antioxidant in the second step are added, and then the dry material (maleic anhydride) is added; after the feeding is finished, the temperature is quickly raised, the distillation temperature is controlled to be not more than 102 ℃, the highest temperature of the material is not more than 205 ℃, when the distillation temperature is lower than 90 ℃, the nitrogen amount is increased to 10 cubic meters per hour, and the reaction is carried out at the constant temperature of 205 ℃. Reacting at constant temperature until the acid value is 28-32 mgKOH/g and the polyester viscosity is 50-55P/120 ℃, and beginning to cool the reaction kettle by taking the polyester viscosity as an end point. When the temperature of the materials is reduced to 180 ℃, adding an auxiliary material polymerization inhibitor, and immediately starting to dilute the materials in the pot (styrene and copper isooctanoate are added into the diluting pot in advance).
The dilution temperature is controlled below 85 ℃.
Table 1 shows the physical properties of resin castings prepared in examples 1-3 and comparative examples.
Table 1: physical Properties of resin casting
| Inspection item | Example 1 resin | Example 2 resin | Example 3 resin | Comparative resin |
| Degree of transparency | Is transparent | Is transparent | Is transparent | Turbid and opaque |
| Tensile strength/MPa | 55.6 | 59 | 65 | 60 |
| Flexural Strength/MPa | 121 | 128 | 134 | 127 |
| Elongation at break/% | 3.1 | 3.4 | 3.9 | 3.2 |
| Impact toughness/kJ/m 2 | 8.0 | 8.6 | 9.5 | 8.9 |
| Heat distortion temperature/. Degree.C | 138 | 130 | 123 | 125 |
The resins prepared in examples 1-3 and comparative examples were formed into SMC/BMC materials and pressed into sheets for performance testing. The test results are shown in tables 2 and 3.
SMC formulation (by weight): 65 parts of resin, 35 parts of low shrinkage agent, 1 part of curing agent, 0.4 part of polymerization inhibitor, 4 parts of zinc stearate, 160 parts of calcium carbonate, 1 part of magnesium oxide paste and 28% of glass fiber.
BMC formulation (by weight): 70 parts of resin, 30 parts of low shrinkage agent, 1 part of curing agent, 0.5 part of polymerization inhibitor, 4.5 parts of zinc stearate, 305 parts of calcium carbonate, 1 part of magnesium oxide paste and 10% of glass fiber content.
Table 2: physical properties of resin SMC
Table 3: physical properties of resin SMC
As can be seen from tables 2 and 3, the SMC/BMC material made with the resin prepared in examples 1-3 has superior physical and mechanical properties to the SMC/BMC material made with the resin synthesized by the conventional two-step process.
Claims (7)
1. The terephthalic acid type unsaturated polyester resin is characterized by being synthesized by a three-step process, wherein a reaction system comprises the following components in percentage by weight: the first step, 14 to 20 percent of terephthalic acid, 18 to 23 percent of methyl propylene glycol, 3 to 4 percent of trimethylolpropane and 0.02 percent of catalyst; step two, 33 to 40 percent of maleic anhydride, 19 to 21 percent of dihydric alcohol and 0.06 to 0.07 percent of antioxidant; step three, 3 percent of maleic anhydride and 0.02 to 0.03 percent of polymerization inhibitor;
the preparation method of the terephthalic acid type unsaturated polyester resin comprises the following steps:
step 1: adding the wet material and the auxiliary agent in the first step, stirring uniformly, adding the dry material under stirring, after the feeding is finished, supplying nitrogen, heating, controlling the distillation temperature to be not more than 103 ℃, controlling the highest material temperature to be not more than 215 ℃, stopping heating and cooling when the sampled material is transparent and the acid value is less than 5 mgKOH/g;
and 2, step: when the temperature of the material is reduced to 180 ℃, adding the wet material and the auxiliary agent in the second step, adding the dry material, heating after the material is added, controlling the distillation temperature to be not more than 102 ℃, controlling the highest temperature of the material to be not more than 205 ℃, increasing the nitrogen amount when the distillation temperature is lower than 90 ℃, reacting at the constant temperature of 205 ℃, controlling the viscosity of the polyester as the end point when the constant temperature reaction is carried out until the acid value is less than 15mgKOH/g and the viscosity of the polyester is 40-42P/120 ℃, and starting to reduce the temperature;
and 3, step 3: when the temperature of the materials is reduced to 180 ℃, adding the polymerization inhibitor and the dry materials in the third step, keeping the temperature at 175-180 ℃ for 1 hour, then reducing the temperature, and diluting with styrene;
the dihydric alcohol is ethylene glycol or propylene glycol or a mixture of the two.
2. The terephthalic acid type unsaturated polyester resin according to claim 1, further comprising styrene in an amount of 30 to 40% based on the sum of styrene and the weight of the reaction system.
3. The terephthalic acid type unsaturated polyester resin according to claim 2, wherein the styrene content is 30 to 31%.
4. The terephthalic-type unsaturated polyester resin according to claim 1, wherein the catalyst is monobutyltin oxide.
5. The terephthalic acid type unsaturated polyester resin according to claim 1, wherein the antioxidant is triphenyl phosphite.
6. The terephthalic-type unsaturated polyester resin according to claim 1, wherein the polymerization inhibitor is methyl hydroquinone.
7. The terephthalic acid type unsaturated polyester resin according to claim 1, wherein the dilution in the step 3 is carried out at a temperature not exceeding 85 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010759554.5A CN111892702B (en) | 2020-07-31 | 2020-07-31 | Terephthalic acid type unsaturated polyester resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010759554.5A CN111892702B (en) | 2020-07-31 | 2020-07-31 | Terephthalic acid type unsaturated polyester resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111892702A CN111892702A (en) | 2020-11-06 |
| CN111892702B true CN111892702B (en) | 2022-12-13 |
Family
ID=73182913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010759554.5A Active CN111892702B (en) | 2020-07-31 | 2020-07-31 | Terephthalic acid type unsaturated polyester resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111892702B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979932B (en) * | 2021-03-08 | 2023-05-30 | 镇江利德尔复合材料有限公司 | Transparent p-benzene type unsaturated polyester resin and application thereof |
| CN115819738A (en) * | 2021-12-28 | 2023-03-21 | 镇江利德尔复合材料有限公司 | Resin for double-wall tank and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL101836C (en) * | 1955-12-24 | |||
| CA987832A (en) * | 1971-07-19 | 1976-04-20 | Teijin Limited | Process for preparation of unsaturated polyester |
| FI990195A (en) * | 1998-09-29 | 2000-03-30 | Neste Oyj | Unsaturated polyester resin and its use |
| JP2000239364A (en) * | 1999-02-25 | 2000-09-05 | Showa Highpolymer Co Ltd | Unsaturated polyester, its production and unsaturated polyester resin |
| US6414085B1 (en) * | 2000-11-22 | 2002-07-02 | Arco Chemical Technology, L.P. | Polyester resins based on terephthalic acid and 2-methyl-1,3-propanediol and processes for the preparation thereof |
| CN1712427A (en) * | 2005-07-12 | 2005-12-28 | 朱友成 | Unsaturated polyester resin for mould pressing and production thereof |
| CN102627740A (en) * | 2012-03-21 | 2012-08-08 | 常州华科树脂有限公司 | Low styrene volatilization unsaturated polyester gel coat resin and preparation method thereof |
| CN103265668B (en) * | 2013-05-21 | 2015-08-12 | 山东宏信化工股份有限公司 | The preparation method of terephthalic unsaturated polyester resin |
| CN104418985A (en) * | 2013-09-11 | 2015-03-18 | 江阴明大化工有限公司 | Method for synthesizing terephthalic type unsaturated polyester resin by utilizing glycerol |
| CN103951792A (en) * | 2014-04-15 | 2014-07-30 | 吴桥昊通树脂有限公司 | Method for producing p-benzenoid unsaturated polyester resin |
| CN108623796B (en) * | 2018-06-07 | 2020-09-29 | 浙江东大树脂科技股份有限公司 | Method for producing p-benzene unsaturated polyester resin by using waste terephthalic acid |
-
2020
- 2020-07-31 CN CN202010759554.5A patent/CN111892702B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111892702A (en) | 2020-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111892702B (en) | Terephthalic acid type unsaturated polyester resin and preparation method thereof | |
| CN115181220B (en) | Preparation method and application of p-benzene type unsaturated polyester resin | |
| CN105330820A (en) | Asymmetric-structure modified epoxy acrylic resin and continuous method synthetic method | |
| CN113024785A (en) | Low dielectric heating induced liquid crystal polymer and preparation method thereof | |
| JPH0144246B2 (en) | ||
| CN110305258B (en) | Diluent based on ferulic acid derivative and unsaturated polyester composite material | |
| CN111978444B (en) | Organic polyacid-based photocuring resin and preparation method and application thereof | |
| CN108623796B (en) | Method for producing p-benzene unsaturated polyester resin by using waste terephthalic acid | |
| CN108948338B (en) | End-capped unsaturated polyester resin and synthesis process thereof | |
| US3957906A (en) | Chemically resistant polyester resins compositions | |
| US3940350A (en) | Moulding compositions based on unsaturated polyesters, copolymerisable vinyl monomers and cellulose esters | |
| WO2023134036A1 (en) | Environment-friendly vinyl ester resin | |
| US4447577A (en) | Emulsions of dicyclopentadiene containing polyesters | |
| US4551489A (en) | Emulsions of dicyclopentadiene containing polyesters | |
| EP1423450B1 (en) | Process for making reactive unsaturated polyester resins from 2-methyl-1,3-propanediol | |
| CN116120535B (en) | Modified unsaturated polyester and preparation method thereof | |
| CN101230131A (en) | Method for preparing thickenable dicyclopentadiene unsaturated polyester resin | |
| CN105315416B (en) | Recyclable organism-based vinyl ester resin and preparation method thereof | |
| KR102545381B1 (en) | Process of Vinylester resins for eco-friendly corrosion resistance pultrusion using recycled polyethyleneterephthalate flake | |
| CN115449064B (en) | Artificial quartz stone unsaturated polyester resin and preparation method thereof | |
| CN102627838B (en) | Laser-markable PET chip and preparation method thereof | |
| CN108084419B (en) | Modified unsaturated polyester resin and preparation method thereof | |
| CN116970130A (en) | Environment-friendly unsaturated polyester resin and preparation method thereof | |
| CN118184898A (en) | Environment-friendly dicyclopentadiene unsaturated polyester resin and preparation method thereof | |
| CN116836375A (en) | Ultraviolet-resistant polyester resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |