CN115819741B - Corrosion-resistant high-strength well lid resin for gas station and preparation method thereof - Google Patents
Corrosion-resistant high-strength well lid resin for gas station and preparation method thereof Download PDFInfo
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- CN115819741B CN115819741B CN202111622596.5A CN202111622596A CN115819741B CN 115819741 B CN115819741 B CN 115819741B CN 202111622596 A CN202111622596 A CN 202111622596A CN 115819741 B CN115819741 B CN 115819741B
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- 239000011347 resin Substances 0.000 title claims abstract description 53
- 230000007797 corrosion Effects 0.000 title claims abstract description 33
- 238000005260 corrosion Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 28
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- 238000000034 method Methods 0.000 claims abstract description 10
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 9
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 9
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- 238000010438 heat treatment Methods 0.000 claims description 9
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 7
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- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 230000002195 synergetic effect Effects 0.000 description 3
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229940120693 copper naphthenate Drugs 0.000 description 2
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical group [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
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- 238000002791 soaking Methods 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
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- 241001330002 Bambuseae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000005609 naphthenate group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Underground Structures, Protecting, Testing And Restoring Foundations (AREA)
Abstract
The invention relates to the field of IPC classified C08G, in particular to corrosion-resistant high-strength well lid resin for a gas station and a preparation method thereof. The corrosion-resistant high-strength well lid resin for the gas station comprises the following raw materials in percentage by mass: 40-50% of short-chain alcohol mixture and 30-40% of unsaturated acid or anhydride mixture; the acid value of the corrosion-resistant high-strength well cover resin of the gas station is 10-15 mgKOH/g. The well lid resin prepared by the method has good mechanical property and thermal deformation temperature, effectively enhances the hydrolysis resistance, acid and alkali corrosion resistance and static resistance of the resin in the outdoor environment well lid application process, is suitable for popularization in the well lid resin field, and has wide development prospect.
Description
Technical Field
The invention relates to the field of IPC classified C08G, in particular to corrosion-resistant high-strength well lid resin for a gas station and a preparation method thereof.
Background
With the development of economy and the improvement of the living standard of people, more families begin to select household sedans for living and traveling, so that gas stations between cities such as spring bamboo shoots after rain are generally established. As protection against accidents increases, facilities near gas stations also tend to be safer.
In recent years, the country upgrades and reforms the gas stations of some national enterprises and civil enterprises, and the composite material inspection well cover is promoted in the process, so that the oil gas can be effectively prevented from leaking out due to good performances, and the accident rate is reduced, wherein the composite material is especially common in polyester resin composite materials.
The prior art (CN 201010193382.6) provides a high-strength polyester composite well lid, the composite material mainly comprises unsaturated polyester resin, heavy calcium carbonate, glass fiber, low shrinkage additive and the like, the patent states that the well lid provided by the composite material has good bearing capacity, impact resistance and wear resistance, but the added filler component of the composite material is easy to form micro cracks and pores in a resin composite system to help penetration of corrosive liquid, and the added components such as calcium carbonate and the like have poor acid and alkali corrosion resistance.
Therefore, there is a need for a polyester-based resin that has excellent corrosion resistance and rapid curing effects in addition to excellent mechanical properties.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides a corrosion-resistant high-strength well lid resin for a gas station, which comprises the following raw materials in percentage by mass: 40-50% of short-chain alcohol mixture and 30-40% of unsaturated acid or anhydride mixture; the acid value of the corrosion-resistant high-strength well cover resin of the gas station is 10-15 mgKOH/g.
As a more preferable scheme, the acid value of the corrosion-resistant high-strength gas station well cover resin is 13-14 mgKOH/g.
As a preferable scheme, the corrosion-resistant high-strength well lid resin for the gas station also comprises 0.001-0.1% of auxiliary agent and the balance of cross-linking agent by mass percent.
As a preferred embodiment, the crosslinking agent is styrene.
As a preferable scheme, the short-chain alcohol is at least two of propylene glycol, ethylene glycol, pentanediol, butanediol, propanol, methanol, dipropylene glycol, isopropanol and neopentyl glycol.
As a preferred embodiment, the short chain alcohols are propylene glycol, dipropylene glycol and isopropanol.
As a preferable scheme, the mass ratio of the propylene glycol, the dipropylene glycol and the isopropanol is 20-25: 10 to 15:10.
as a more preferable scheme, the mass ratio of the propylene glycol, the dipropylene glycol and the isopropanol is 23:12:10.
as a preferable embodiment, the unsaturated acid or acid anhydride is any two of isophthalic acid, acrylic anhydride and maleic anhydride.
As a preferred embodiment, the unsaturated acid or anhydride is isophthalic acid or maleic anhydride.
As a preferable scheme, the mass ratio of the isophthalic acid to the maleic anhydride is 7 to 7.5: 28-30 parts.
As a more preferable mode, the mass ratio of the isophthalic acid to the maleic anhydride is 7.5:27.5.
as a more preferred embodiment, the mass ratio of the short chain alcohol mixture to the unsaturated acid or anhydride mixture is 42-48: 33 to 37.
As a more preferred embodiment, the mass ratio of the short chain alcohol mixture to the unsaturated acid or anhydride mixture is 45:35.
in the method, the hydrolysis resistance and corrosion resistance of the resin material can be effectively improved by compounding the specific short-chain alcohol mixture, the unsaturated acid or anhydride mixture and the specific compounding ratio. The applicant believes that: the propylene glycol, the dipropylene glycol, the isopropanol, the isophthalic acid and the maleic anhydride which are selected to be used in the application and have specific compounding ratio are matched with the styrene, and the mass ratio of the two systems is 45: and when 35, uniform long resin chains can be formed in the synthetic process of the resin, so that the aggregation phenomenon of active groups caused by the difference of reactivity ratios of the monomers used in the compounding in the synthetic process can be effectively reduced, chains of the active groups are uniformly dispersed, chain segments of double bond structures at two ends of a molecular chain are effectively formed, the integral content of secondary hydroxyl groups is increased, the number of ester bonds in unit content is greatly reduced, the wettability and the cohesiveness of the resin to glass fibers and other materials are improved, and the resin has a more alkali resistance effect.
As a preferable scheme, the auxiliary agent is at least one of filler, catalyst, antioxidant, flame retardant, ultraviolet resistant absorbent and flame retardant.
As a preferable scheme, the filler is at least one of metal oxide, carbon material and fiber material.
As a preferable embodiment, the flame retardant is at least one of a phosphorus flame retardant and a metal oxide flame retardant.
As a preferable embodiment, the ultraviolet resistant absorber is at least one of salicylic acid, benzophenone, and benzotriazole.
As a preferable scheme, the antioxidant is at least one of phenolic antioxidants and hindered amine antioxidants.
As a preferable scheme, the antioxidant is 2, 6-di-tert-butyl-p-cresol and hydroquinone; the mass ratio of the 2, 6-di-tert-butyl-p-cresol to the hydroquinone is 1-3: 4 to 5.
As a more preferable scheme, the mass ratio of the 2, 6-di-tert-butyl-p-cresol to the hydroquinone is 3:4.
in the application, when the mass ratio of the 2, 6-di-tert-butyl-p-cresol to the hydroquinone added in the application is 3:4, the epoxy resin has good oxidation resistance, and the corrosion resistance and the antistatic property of the resin can be effectively improved. The applicant speculates that: at the moment, the synergistic effect of the 2, 6-di-tert-butyl-p-cresol and hydroquinone can simultaneously capture active free electrons in the resin to change the active free electrons into inactive electrons, so that continuous electron loss reaction is inhibited, and the number of free electrons in the whole system of the resin is reduced; meanwhile, the two can be added to generate a synergistic crosslinking effect with styrene and polyester resin added into the matrix resin, so that a phenol chain segment is introduced into the resin system, the crosslinking density is enhanced, and the number of movable groups in the resin system is reduced.
As a preferred embodiment, the catalyst is at least one of metal naphthenate.
As a preferred embodiment, the catalyst is copper naphthenate.
As a preferable scheme, the viscosity of the corrosion-resistant high-strength well cover resin for the gas station is 1200-1400 mPa.s and 23 ℃.
As a preferable scheme, the viscosity of the corrosion-resistant high-strength well cover resin for the gas station is 1300 mPas and 23 ℃.
According to the well lid resin for the gas station, through the synergistic interaction of the selected specific alcohol, anhydride and styrene raw materials and the specific auxiliary agent, the stable molecular long chain with double-end double bonds is formed, so that the resin has excellent curing activity, the proportion is regulated and controlled in a trace manner, the number of ester bonds, the number of methyl beside the ester bonds and the number of secondary hydroxyl groups in a resin system are controlled, and therefore the resin material with obvious acid and alkali resistance and good mechanical strength and hydrolysis resistance is formed in a synergistic manner.
The second aspect of the invention provides a method for preparing the corrosion-resistant high-strength well lid resin for a gas station, which comprises the following steps: (1) Adding a short-chain alcohol mixture and an unsaturated acid or anhydride mixture raw material into a reaction container, heating and refluxing for reaction under the protection of nitrogen, heating to 140-160 ℃, and refluxing for reaction until the acid value is less than 50mgKOH/g; (2) Gradually heating to 210-230 ℃ to perform polycondensation reaction for 3-4 hours to obtain an intermediate product after the reaction is completed; (3) And adding a cross-linking agent, an auxiliary agent and the cross-linking agent into the intermediate product, and cooling until the viscosity of the product reaches a specified acid value.
As a preferred embodiment, the viscosity of the intermediate product is 1000 to 1150 mPas, 150 ℃.
As a preferred embodiment, the acid value of the intermediate product is 25 to 30mgKOH/g.
The beneficial effects are that:
1. according to the well lid resin for the gas station, which is prepared in the application, the specific short-chain alcohol mixture, the unsaturated acid or anhydride mixture and the specific compound ratio are selected for compounding, so that the hydrolysis resistance and corrosion resistance of a resin material can be effectively improved, the environmental applicability and the service performance of the well lid for the gas station are greatly improved, and the potential safety hazard is reduced.
2. According to the well lid resin for the gas station, when the mass ratio of the 2, 6-di-tert-butyl-p-cresol to the hydroquinone added in the well lid resin is 3:4, the well lid resin not only has good oxidation resistance, but also can effectively improve the corrosion resistance and antistatic property of the resin. The resin material has long service life, excellent stability in long-term use, reduced damage phenomenon, and good practicability and economy.
3. The filling station well lid resin prepared in this application is different from current well lid resin, because its body shows excellent acid and alkali resistant effect, mechanical strength and hydrolysis resistance, can form effectual guard action in the raw materials mixed use such as packing to reduce the holistic damage phenomenon of combined material.
Detailed Description
Example 1
Embodiment 1 in a first aspect provides a corrosion-resistant high-strength well lid resin for a gas station, wherein the raw materials comprise the following components in percentage by mass: 45% of short-chain alcohol mixture, 35% of unsaturated acid or anhydride mixture, 0.1% of auxiliary agent and the balance of cross-linking agent.
Wherein the acid value of the corrosion-resistant high-strength well lid resin of the gas station is 14mgKOH/g; the viscosity was 1300 mPas, 23 ℃.
The short-chain alcohol mixture is a mixture of propylene glycol, dipropylene glycol and isopropanol, and the mass ratio is 23:12:10.
unsaturated acid or anhydride is isophthalic acid and maleic anhydride, and the mass ratio is 7.5:27.5.
the auxiliary agent is antioxidant 0.09% and catalyst 0.01%; the antioxidant is 2, 6-di-tert-butyl-p-cresol and hydroquinone, and the mass ratio is 3:4, a step of; the catalyst is copper naphthenate.
The cross-linking agent is styrene.
The second aspect also provides a preparation method of the corrosion-resistant high-strength filling station well lid resin, which comprises the following steps: (1) Adding a short-chain alcohol mixture and an unsaturated acid or anhydride mixture raw material into a reaction container, heating and refluxing for reaction under the protection of nitrogen, heating to 150 ℃, and refluxing for reaction until the acid value is less than 50mgKOH/g; (2) Gradually heating to 220 ℃, carrying out polycondensation reaction for 3 hours, and obtaining an intermediate product after the reaction is completed; (3) And adding an auxiliary agent and a cross-linking agent into the intermediate product, and cooling until the viscosity of the product reaches a specified acid value.
Wherein the viscosity of the intermediate product is 1100 mPas, 150 ℃; the acid value was 28mgKOH/g.
Example 2
The specific implementation of this example is the same as example 1, except that: the short chain alcohol mixture was 42% and the unsaturated acid or anhydride mixture was 37%.
Example 3
The specific implementation of this example is the same as example 1, except that: the mass ratio of propylene glycol, dipropylene glycol and isopropanol is 20:15:10.
comparative example 1
The specific embodiment of this comparative example is the same as example 1, except that: the short chain alcohol mixture was 20% and the unsaturated acid or anhydride mixture was 40%.
Comparative example 2
The specific embodiment of this comparative example is the same as example 1, except that: the mass ratio of the propylene glycol, the dipropylene glycol and the isopropanol is 1:1:1.
evaluation of Performance
1. Mechanical properties: the tensile properties and flexural properties of the resin casting were tested with reference to the standard GB/T2567, 5 specimens were tested for each comparative example, and the average of the values measured is reported in Table 1.
2. Heat distortion temperature: the heat distortion temperature of the resin casting was tested with reference to the standard of GB/T1634.1, 5 samples were tested for each comparative example, and the average of the measured values is reported in Table 2.
3. Corrosion resistance: respectively soaking the samples in a.10% sodium hydroxide solution at 95 ℃ for 50 hours; b, the test of flexural strength retention was carried out according to GB/T2567 standard by soaking in 50% sulfuric acid solution at 80℃for 28d, 5 samples were tested for each comparative example, and the average of the values obtained is reported in Table 2.
TABLE 1
| Examples | Tensile strength MPa | Elongation at break% | Flexural Strength MPa |
| Example 1 | 99.8 | 10.4 | 184.3 |
| Example 2 | 94.6 | 9.4 | 183.9 |
| Example 3 | 95.7 | 9.6 | 179.4 |
| Comparative example 1 | 78.6 | 6.5 | 141.5 |
| Comparative example 2 | 80.1 | 6.2 | 139.3 |
TABLE 1
It can be known from examples 1-3, comparative examples 1-2 and tables 1 and 2 that the corrosion-resistant high-strength well lid resin for the gas station and the preparation process thereof provided by the invention have good mechanical properties and thermal deformation temperature, effectively enhance the hydrolysis resistance, acid and alkali corrosion resistance and static resistance of the resin in the outdoor environment well lid application process, are suitable for popularization in the well lid resin field, and have wide development prospects. Wherein example 1 obtained the best performance index under the factors of the best preparation raw material proportion and preparation process.
Claims (4)
1. The utility model provides a corrosion-resistant high strength filling station well lid resin which characterized in that: the raw materials at least comprise the following components in percentage by mass: 40-50% of a short-chain alcohol mixture, and 30-40% of an unsaturated acid or anhydride mixture; the acid value of the corrosion-resistant high-strength gas station well lid resin is 10-15 mgKOH/g;
the corrosion-resistant high-strength well lid resin for the gas station also comprises 0.001-0.1% of auxiliary agent and the balance of cross-linking agent in percentage by mass;
the auxiliary agent is at least one of a filler, a catalyst, an antioxidant, a flame retardant, an ultraviolet-resistant absorbent and a flame retardant;
the antioxidant is 2, 6-di-tert-butyl-p-cresol and hydroquinone; the mass ratio of the 2, 6-di-tert-butyl-p-cresol to the hydroquinone is 1-3: 4-5;
the short-chain alcohol is propylene glycol, dipropylene glycol and isopropanol; the mass ratio of the propylene glycol, the dipropylene glycol and the isopropanol is 20-25: 10-15: 10;
the unsaturated acid or anhydride is isophthalic acid and maleic anhydride; the mass ratio of the isophthalic acid to the maleic anhydride is 7-7.5: 28-30.
2. The corrosion resistant high strength service station well lid resin of claim 1, wherein: the catalyst is at least one of naphthenic acid metal salts.
3. The corrosion resistant high strength service station well lid resin of claim 2, wherein: the viscosity of the corrosion-resistant high-strength well lid resin of the gas station is 1200-1400 mPas and is 23 ℃.
4. A method for preparing the corrosion-resistant high-strength well lid resin for a gas station according to any one of claims 1 to 3, which is characterized in that: the method comprises the following steps: (1) Adding a short-chain alcohol mixture and an unsaturated acid or anhydride mixture raw material into a reaction container, heating and refluxing under the protection of nitrogen, heating to 140-160 ℃, and refluxing until the acid value is less than 50mgKOH/g; (2) Gradually heating to 210-230 ℃, carrying out polycondensation reaction for 3-4 hours, and obtaining an intermediate product after the reaction is completed; (3) And adding an auxiliary agent and a cross-linking agent into the intermediate product, and cooling until the viscosity of the product reaches a specified acid value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111622596.5A CN115819741B (en) | 2021-12-28 | 2021-12-28 | Corrosion-resistant high-strength well lid resin for gas station and preparation method thereof |
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| CN202111622596.5A CN115819741B (en) | 2021-12-28 | 2021-12-28 | Corrosion-resistant high-strength well lid resin for gas station and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1419973A (en) * | 1971-12-10 | 1975-12-31 | Koppers Co Inc | Chemically resistand polyesters |
| CN103626931A (en) * | 2013-11-29 | 2014-03-12 | 浙江天和树脂有限公司 | Low-cost corrosion-resistant unsaturated polyester resin, and preparation method and use thereof |
| CN112851875A (en) * | 2021-03-05 | 2021-05-28 | 镇江利德尔复合材料有限公司 | Low-smoke low-toxicity halogen-free flame-retardant resin and preparation method and application thereof |
-
2021
- 2021-12-28 CN CN202111622596.5A patent/CN115819741B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1419973A (en) * | 1971-12-10 | 1975-12-31 | Koppers Co Inc | Chemically resistand polyesters |
| CN103626931A (en) * | 2013-11-29 | 2014-03-12 | 浙江天和树脂有限公司 | Low-cost corrosion-resistant unsaturated polyester resin, and preparation method and use thereof |
| CN112851875A (en) * | 2021-03-05 | 2021-05-28 | 镇江利德尔复合材料有限公司 | Low-smoke low-toxicity halogen-free flame-retardant resin and preparation method and application thereof |
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| CN115819741A (en) | 2023-03-21 |
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