A modified PVB resin and its preparation method
By introducing fluorinated acetal monoaldehyde derivatives and glyoxal crosslinking agents into PVB resin, a strongly hydrophobic layer and micro-crosslinked structure are formed, which solves the problem of performance degradation of PVB resin under ultraviolet and humid environments and improves weather resistance and stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- 江西天城高新材料有限公司
- Filing Date
- 2026-04-01
- Publication Date
- 2026-05-26
AI Technical Summary
PVB resin is prone to yellowing and molecular chain breakage under strong ultraviolet light, and it is also prone to absorbing water and turning white in humid environments, which leads to the deterioration of optical and mechanical properties.
By introducing fluorinated acetal monoaldehyde derivatives and glyoxal crosslinking agents, a strong hydrophobic layer and micro-crosslinked structure are formed, enhancing the weather resistance and stability of the resin and preventing yellowing and deterioration of mechanical properties.
It effectively shields against external corrosive media, reduces the oxidation rate, improves the resin's UV resistance and water resistance, and keeps its optical properties unaffected.
Smart Images
Figure CN122080264A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of polymer material synthesis technology, specifically to a modified PVB resin and its preparation method. Background Technology
[0002] PVB resin is a linear long-chain resin with high transparency, strong adhesion, and high toughness. It is often used in the automotive, construction, and various electronics industries, such as in 3D printing materials and interlayers in laminated glass. Although PVB resin has good UV resistance, long-term exposure to strong UV environments can still cause slight yellowing and molecular chain breakage, thus affecting the resin's optical properties. Furthermore, PVB resin contains a large number of hydroxyl groups, making it prone to absorbing water and turning white in humid environments. Hydrolysis can further increase the number of hydroxyl groups and degrade mechanical properties. Therefore, it is necessary to study these defects of PVB resin to meet market demands. Summary of the Invention
[0003] The purpose of this invention is to provide a modified PVB resin and its preparation method to solve the defects of PVB resin in terms of insufficient resistance to ultraviolet radiation and poor resistance to water vapor, salt and alkali corrosion.
[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution:
[0005] In a first aspect, the present invention provides a method for preparing a modified PVB resin, comprising the following steps:
[0006] 2-Amino-1,3-propanediol was mixed with anhydrous methanol, then triethylamine and epifluoropropane were added. After heating and reacting, the solvent was removed by rotary evaporation to obtain a fluorinated propanediol derivative.
[0007] The fluorinated propylene glycol derivative was mixed with anhydrous methanol, the pH was adjusted, and then glyoxal aqueous solution was added. After heating and reacting, sodium hydroxide was added to neutralize the mixture. The solvent was removed by rotary evaporation and the mixture was filtered to obtain the fluorinated acetal monoaldehyde derivative.
[0008] A fluorinated acetal monoaldehyde derivative was mixed with n-butyraldehyde and glyoxal to obtain an aldehyde mixture.
[0009] Polyvinyl alcohol (PVA) was mixed with deionized water to prepare an aqueous PVA solution. An antioxidant was added, the pH was adjusted, an aldehyde mixture was added, and the mixture was heated to react. Sodium hydroxide solution was added to neutralize the reaction system and terminate the reaction. The neutralized reaction system was centrifuged, and the centrifuged product was washed with deionized water and dried to obtain modified PVB resin.
[0010] Furthermore, in step S1, the mass ratio of 2-amino-1,3-propanediol, triethylamine, and epifluoropropane is 1:(0.06~0.11):(0.83~0.91).
[0011] Furthermore, after adding triethylamine, the reaction system needs to be cooled to 0~10℃ before adding epifluoropropylene dropwise.
[0012] During the heating reaction, the heating temperature is 30~45℃, and the stirring reaction time is 3~5h;
[0013] After removing the solvent by rotary evaporation, the remaining product should be washed with deionized water at a temperature of 0~4℃ and then vacuum dried.
[0014] Furthermore, the mass ratio of the fluorinated propylene glycol derivative to glyoxal is (3~3.1):1.
[0015] Furthermore, hydrochloric acid was used to adjust the pH value to 2-3;
[0016] When adding glyoxal aqueous solution, the reaction system should be cooled to 0~10℃ before adding the glyoxal aqueous solution dropwise.
[0017] During the heating reaction, the heating temperature is 25~35℃, and the stirring reaction time is 4~6h.
[0018] Furthermore, the mass ratio of the fluorinated acetal monoaldehyde derivative to n-butyraldehyde and glyoxal is (1~2):(6.4~7):(0.04~0.08).
[0019] Furthermore, the concentration of the polyvinyl alcohol aqueous solution is 10-15 wt%; the antioxidant is at least one of antioxidant 1010, antioxidant BHT and antioxidant 168.
[0020] Furthermore, when adjusting the pH value, hydrochloric acid is used to adjust the pH value of the reaction system to 1~3;
[0021] During the heating reaction, the heating temperature is 30~50℃, and the reaction is stirred for 2~4 hours.
[0022] Furthermore, the mass ratio of the polyvinyl alcohol, antioxidant, and aldehyde mixture is 100:(0.3~0.5):(60~70).
[0023] Secondly, the present invention also provides a modified PVB resin, which is prepared by the above method.
[0024] Compared with the prior art, the beneficial effects achieved by this invention are as follows: To solve the defects of insufficient UV resistance and water resistance of PVB resin, this invention introduces a fluorinated acetal monoaldehyde derivative containing fluorine into the PVB resin. This invention first uses 2-amino-1,3-propanediol and epifluoropropane as raw materials. Under alkaline catalysis of triethylamine and low-temperature dropwise addition conditions of 0-10°C, a ring-opening reaction occurs between the amino and epoxy groups, thereby preparing a fluoropropanediol derivative containing fluorine and a propylene glycol structure. Then, it is combined with... Glyoxal is mixed and reacted. By controlling the reaction conditions, a fluorinated acetal monoaldehyde derivative containing fluorine and free aldehyde groups is generated. Then, it is mixed with n-butyraldehyde and glyoxal to undergo an acetalization reaction with the 1,3-o-diol structure of the PVA molecular chain, thus incorporating the fluorinated side link into the PVB molecular chain. Utilizing the high electronegativity of fluorine atoms and the extremely high bond energy of CF bonds, a strong hydrophobic layer can be formed in the PVB resin, thereby shielding it from the intrusion of external corrosive media, blocking the contact between oxygen and water molecules and the interior of the resin, significantly reducing the oxidation rate of residual hydroxyl groups in PVB, and preventing the oxidation of hydroxyl groups to generate carbonyl, carboxyl, and other chromogenic groups. This inhibits oxidative yellowing from the source, improving weather resistance. Therefore, it can effectively avoid yellowing when used as an interlayer in laminated glass and mechanical property degradation caused by external moisture environment when used as a 3D printing material.
[0025] Furthermore, the fluorinated acetal monoaldehyde derivative introduced in this invention is a short-chain fluorine monomer and does not contain chromophores. Therefore, it can effectively avoid the negative impact of the fluorinated acetal monoaldehyde derivative on the optical properties of PVB resin. In addition, the fluorinated acetal monoaldehyde derivative introduced in this invention contains an acetal structure and a polyol structure, which is similar to the structure of PVB resin. This can effectively reduce phase separation between different components, thereby reducing particle scattering and not affecting the haze of PVB resin too much.
[0026] Building upon this foundation, the present invention further introduces glyoxal as a crosslinking agent into PVB resin. Glyoxal contains dialdehyde groups, both of which exhibit high reactivity. Moreover, the reactivity of both is higher than that of free aldehyde groups and n-butyraldehyde, which are derivatives of fluorinated acetal monoaldehyde groups. In an acidic catalytic environment, glyoxal preferentially undergoes intermolecular acetalization reactions with 1,3-o-diol structures on different PVA molecular chains. Each glyoxal molecule connects two adjacent PVA molecular chains through two acetal bonds, forming an intermolecular cyclic acetal crosslinking structure. This transforms the originally linear PVB molecular chains into a slightly network structure, enhancing the stability of the resin and thus improving its shielding performance. This further reduces the intrusion of external corrosive media and enhances the stability of the PVB resin.
[0027] Furthermore, to avoid excessive cross-linking that would reduce the toughness and increase the brittleness of PVB resin, this invention also strictly limits the amount of glyoxal added, making its addition amount much lower than that of n-butyraldehyde, thereby avoiding excessive cross-linking. Attached Figure Description
[0028] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings:
[0029] Figure 1 This is a picture of the finished PVB resin prepared in Example 1 of the present invention;
[0030] Figure 2 This is the chemical reaction equation for step S1 of the present invention;
[0031] Figure 3 This is the chemical reaction equation for step S2 of the present invention. Detailed Implementation
[0032] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0033] In the embodiments and comparative examples of this invention, the polyvinyl alcohol used is polyvinyl alcohol 1899; the plasticizer used is dioctyl sebacate; the nano oxide used is TH-8200S type fumed silica; and the titanate coupling agent used is titanate coupling agent 201.
[0034] Example 1
[0035] A method for preparing a modified PVB resin includes the following steps:
[0036] S1. Under nitrogen protection, 2-amino-1,3-propanediol was dispersed in anhydrous methanol and stirred until homogeneous. Triethylamine was then added and mixed thoroughly. The reaction system was cooled to 4°C, and epifluoropropylene was added dropwise. After the addition was complete, the temperature was raised to 30°C, and the reaction was stirred for 5 hours. Excess solvent was removed by rotary evaporation. The reaction product was washed with deionized water at 2°C and then evaporated under vacuum to constant weight to obtain the fluoropropanediol derivative. The reaction equation is as follows: Figure 2 As shown;
[0037] The mass ratio of 2-amino-1,3-propanediol, triethylamine, and epifluoropropane is 1:0.06:0.83.
[0038] S2. The fluoropropylene glycol derivative was dispersed in anhydrous methanol and stirred until completely dissolved. Hydrochloric acid was added to adjust the pH of the reaction system to 3. The reaction system was then cooled to 4°C. An aqueous solution of glyoxal containing glyoxal was added dropwise. After the addition was completed, the system was protected under a nitrogen atmosphere and heated to 25°C. The reaction was stirred for 6 hours. Sodium hydroxide was added dropwise to neutralize the pH to neutral. Excess solvent was removed by rotary evaporation and the mixture was filtered to obtain the fluoroacetal monoaldehyde derivative.
[0039] The mass ratio of the fluorinated propylene glycol derivative to glyoxal is 3:1; the reaction equation is as follows. Figure 3 As shown;
[0040] S3. Mix the fluorinated acetal monoaldehyde derivative with n-butyraldehyde and glyoxal to obtain an aldehyde mixture;
[0041] The mass ratio of the fluorinated acetal monoaldehyde derivative to n-butyraldehyde and glyoxal is 1:7:0.04.
[0042] S4. Mix polyvinyl alcohol with deionized water, heat to 90°C, and stir until completely dissolved to prepare a 10wt% polyvinyl alcohol aqueous solution.
[0043] After adding antioxidant 1010, add hydrochloric acid to adjust the pH to 3, then slowly add aldehyde mixture dropwise. After the addition is complete, heat to 30°C, keep the reaction at this temperature for 4 hours, and then add sodium hydroxide solution to neutralize the reaction system and terminate the reaction.
[0044] The neutralized reaction system was centrifuged, and the centrifuged product was washed multiple times with deionized water. After vacuum dehydration and drying at 60°C, the modified PVB resin was obtained.
[0045] The mass ratio of the polyvinyl alcohol, antioxidant 1010, and aldehyde mixture is 100:0.3:60; the actual product is as follows: Figure 1 As shown.
[0046] Example 2
[0047] Compared with Example 1, this example increases the amount of triethylamine and epifluoropropane added in step S1, while the parameters of the remaining steps are the same as those in Example 1.
[0048] A method for preparing a modified PVB resin includes the following steps:
[0049] S1. Under nitrogen protection, 2-amino-1,3-propanediol was dispersed in anhydrous methanol and stirred until homogeneous. Triethylamine was then added and mixed until homogeneous. The reaction system was cooled to 4°C, and epifluoropropylene was added dropwise. After the addition was complete, the temperature was raised to 30°C, and the reaction was stirred for 5 hours. Excess solvent was removed by rotary evaporation. The reaction product was washed with low-temperature deionized water at 2°C and then vacuum evaporated to constant weight to obtain the fluorinated propanediol derivative.
[0050] The mass ratio of 2-amino-1,3-propanediol, triethylamine, and epifluoropropane is 1:0.11:0.91.
[0051] Example 3
[0052] Compared with Example 2, this example increases the amount of fluorinated propylene glycol derivative added in step S2, while the remaining steps are the same as in Example 2;
[0053] A method for preparing a modified PVB resin includes the following steps:
[0054] S1. Under nitrogen protection, 2-amino-1,3-propanediol was dispersed in anhydrous methanol and stirred until homogeneous. Triethylamine was then added and mixed until homogeneous. The reaction system was cooled to 4°C, and epifluoropropylene was added dropwise. After the addition was complete, the temperature was raised to 30°C, and the reaction was stirred for 5 hours. Excess solvent was removed by rotary evaporation. The reaction product was washed with low-temperature deionized water at 2°C and then vacuum evaporated to constant weight to obtain the fluorinated propanediol derivative.
[0055] The mass ratio of 2-amino-1,3-propanediol, triethylamine, and epifluoropropane is 1:0.06:0.91.
[0056] S2. The fluoropropylene glycol derivative was dispersed in anhydrous methanol and stirred until completely dissolved. Hydrochloric acid was added to adjust the pH of the reaction system to 3. The reaction system was then cooled to 4°C. An aqueous solution of glyoxal containing glyoxal was added dropwise. After the addition was completed, the system was protected under a nitrogen atmosphere and heated to 25°C. The reaction was stirred for 6 hours. Sodium hydroxide was added dropwise to neutralize the pH to neutral. Excess solvent was removed by rotary evaporation and the mixture was filtered to obtain the fluoroacetal monoaldehyde derivative.
[0057] The mass ratio of fluorinated propylene glycol derivative to glyoxal is 3.1:1.
[0058] Example 4
[0059] Compared with Example 1, the amount of fluorinated acetal monoaldehyde derivative added in step S3 of this example is increased, the amount of n-butyraldehyde added is decreased, and the other parameters are the same as those in Example 1.
[0060] A method for preparing a modified PVB resin includes the following steps:
[0061] S3. Mix the fluorinated acetal monoaldehyde derivative with n-butyraldehyde and glyoxal to obtain an aldehyde mixture;
[0062] The mass ratio of the fluorinated acetal monoaldehyde derivative to n-butyraldehyde and glyoxal is 2:6.4:0.04.
[0063] S4. Mix polyvinyl alcohol with deionized water, heat to 90°C, and stir until completely dissolved to prepare a 10wt% polyvinyl alcohol aqueous solution.
[0064] After adding antioxidant 1010, add hydrochloric acid to adjust the pH to 3, then slowly add aldehyde mixture dropwise. After the addition is complete, heat to 30°C, keep the reaction at this temperature for 4 hours, and then add sodium hydroxide solution to neutralize the reaction system and terminate the reaction.
[0065] The neutralized reaction system was centrifuged, and the centrifuged product was washed multiple times with deionized water. After vacuum dehydration and drying at 60°C, the modified PVB resin was obtained.
[0066] The mass ratio of polyvinyl alcohol, antioxidant 1010, and aldehyde mixture is 100:0.3:60.
[0067] Example 5
[0068] Compared with Example 1, this example increases the amount of glyoxal and n-butyraldehyde added in step S3;
[0069] A method for preparing a modified PVB resin includes the following steps:
[0070] S3. Mix the fluorinated acetal monoaldehyde derivative with n-butyraldehyde and glyoxal to obtain an aldehyde mixture;
[0071] The mass ratio of the fluorinated acetal monoaldehyde derivative to n-butyraldehyde and glyoxal is 1:7:0.08.
[0072] S4. Mix polyvinyl alcohol with deionized water, heat to 90°C, and stir until completely dissolved to prepare a 10wt% polyvinyl alcohol aqueous solution.
[0073] After adding antioxidant 1010, add hydrochloric acid to adjust the pH to 3, then slowly add aldehyde mixture dropwise. After the addition is complete, heat to 30°C, keep the reaction at this temperature for 4 hours, and then add sodium hydroxide solution to neutralize the reaction system and terminate the reaction.
[0074] The neutralized reaction system was centrifuged, and the centrifuged product was washed multiple times with deionized water. After vacuum dehydration and drying at 60°C, the modified PVB resin was obtained.
[0075] The mass ratio of polyvinyl alcohol, antioxidant 1010, and aldehyde mixture is 100:0.3:60.
[0076] Example 6
[0077] A method for preparing a modified PVB resin includes the following steps:
[0078] S1. Under nitrogen protection, 2-amino-1,3-propanediol was dispersed in anhydrous methanol and stirred until homogeneous. Triethylamine was then added and mixed until homogeneous. The reaction system was cooled to 4°C, and fluoropropylene oxide was added dropwise. After the addition was complete, the temperature was raised to 45°C, and the reaction was stirred for 3 hours. Excess solvent was removed by rotary evaporation. The reaction product was washed with low-temperature deionized water at 2°C and then vacuum evaporated to constant weight to obtain a fluoropropylene glycol derivative.
[0079] The mass ratio of 2-amino-1,3-propanediol, triethylamine, and epifluoropropane is 1:0.06:0.83.
[0080] S2. The fluoropropylene glycol derivative was dispersed in anhydrous methanol and stirred until completely dissolved. Hydrochloric acid was added to adjust the pH of the reaction system to 2. The reaction system was then cooled to 4°C. An aqueous solution of glyoxal containing glyoxal was added dropwise. After the addition was completed, the system was protected under a nitrogen atmosphere and heated to 35°C. The reaction was stirred for 4 hours. Sodium hydroxide was added dropwise to neutralize the pH to neutral. Excess solvent was removed by rotary evaporation and the mixture was filtered to obtain the fluoroacetal monoaldehyde derivative.
[0081] The mass ratio of fluorinated propylene glycol derivatives to glyoxal is 3:1.
[0082] S3. Mix the fluorinated acetal monoaldehyde derivative with n-butyraldehyde and glyoxal to obtain an aldehyde mixture;
[0083] The mass ratio of the fluorinated acetal monoaldehyde derivative to n-butyraldehyde and glyoxal is 1:7:0.04.
[0084] S4. Mix polyvinyl alcohol with deionized water, heat to 90°C, and stir until completely dissolved to prepare a 15wt% polyvinyl alcohol aqueous solution.
[0085] After adding antioxidant 1010, add hydrochloric acid to adjust the pH to 1, then slowly add aldehyde mixture dropwise. After the addition is complete, heat to 50°C, keep the reaction at this temperature for 2 hours, and then add sodium hydroxide solution to neutralize the reaction system and terminate the reaction.
[0086] The neutralized reaction system was centrifuged, and the centrifuged product was washed multiple times with deionized water. After vacuum dehydration and drying at 60°C, the modified PVB resin was obtained.
[0087] The mass ratio of polyvinyl alcohol, antioxidant 1010, and aldehyde mixture is 100:0.5:70.
[0088] Example 7
[0089] A method for preparing a modified PVB resin includes the following steps:
[0090] S1. Under nitrogen protection, 2-amino-1,3-propanediol was dispersed in anhydrous methanol and stirred until homogeneous. Triethylamine was then added and mixed until homogeneous. The reaction system was cooled to 4°C, and epifluoropropylene was added dropwise. After the addition was complete, the temperature was raised to 40°C, and the reaction was stirred for 4 hours. Excess solvent was removed by rotary evaporation. The reaction product was washed with low-temperature deionized water at 2°C and then vacuum evaporated to constant weight to obtain the fluorinated propanediol derivative.
[0091] The mass ratio of 2-amino-1,3-propanediol, triethylamine, and epifluoropropane is 1:0.09:0.87.
[0092] S2. The fluorinated propylene glycol derivative was dispersed in anhydrous methanol and stirred until completely dissolved. Hydrochloric acid was added to adjust the pH of the reaction system to 2.5. The reaction system was then cooled to 4°C. An aqueous solution of glyoxal containing glyoxal was added dropwise. After the addition was complete, the system was protected under a nitrogen atmosphere and heated to 30°C. The reaction was stirred for 5 hours. Sodium hydroxide was added dropwise to neutralize the pH to neutral. Excess solvent was removed by rotary evaporation and the mixture was filtered to obtain the fluorinated acetal monoaldehyde derivative.
[0093] The mass ratio of fluorinated propylene glycol derivatives to glyoxal is 3:1.
[0094] S3. Mix the fluorinated acetal monoaldehyde derivative with n-butyraldehyde and glyoxal to obtain an aldehyde mixture;
[0095] The mass ratio of the fluorinated acetal monoaldehyde derivative to n-butyraldehyde and glyoxal is 1:6.7:0.06.
[0096] S4. Mix polyvinyl alcohol with deionized water, heat to 90°C, and stir until completely dissolved to prepare a 15wt% polyvinyl alcohol aqueous solution.
[0097] After adding antioxidant 1010, add hydrochloric acid to adjust the pH to 2, then slowly add aldehyde mixture dropwise. After the addition is complete, heat to 40°C, keep the reaction at this temperature for 3 hours, and then add sodium hydroxide solution to neutralize the reaction system and terminate the reaction.
[0098] The neutralized reaction system was centrifuged, and the centrifuged product was washed multiple times with deionized water. After vacuum dehydration and drying at 60°C, the modified PVB resin was obtained.
[0099] The mass ratio of polyvinyl alcohol, antioxidant 1010, and aldehyde mixture is 100:0.5:70.
[0100] Comparative Example 1
[0101] Compared with Example 1, no fluorinated acetal monoaldehyde derivative was prepared in this comparative example;
[0102] A method for preparing a modified PVB resin includes the following steps:
[0103] S1. Mix n-butyraldehyde and glyoxal to obtain an aldehyde mixture;
[0104] The mass ratio of n-butyraldehyde to glyoxal is 7:0.04.
[0105] S2. Mix polyvinyl alcohol with deionized water, heat to 90°C, and stir until completely dissolved to prepare a 10wt% polyvinyl alcohol aqueous solution.
[0106] After adding antioxidant 1010, add hydrochloric acid to adjust the pH to 3, then slowly add aldehyde mixture dropwise. After the addition is complete, heat to 30°C, keep the reaction at this temperature for 4 hours, and then add sodium hydroxide solution to neutralize the reaction system and terminate the reaction.
[0107] The neutralized reaction system was centrifuged, and the centrifuged product was washed multiple times with deionized water. After vacuum dehydration and drying at 60°C, the modified PVB resin was obtained.
[0108] The mass ratio of polyvinyl alcohol, antioxidant 1010, and aldehyde mixture is 100:0.3:60.
[0109] Comparative Example 2
[0110] Compared with Example 1, glyoxal was not added in step S3 of this comparative example, and the remaining steps were the same as in Example 1;
[0111] A method for preparing a modified PVB resin includes the following steps:
[0112] S3. Mix the fluorinated acetal monoaldehyde derivative with n-butyraldehyde to obtain an aldehyde mixture;
[0113] The mass ratio of the fluorinated acetal monoaldehyde derivative to n-butyraldehyde is 1:7.
[0114] S4. Mix polyvinyl alcohol with deionized water, heat to 90°C, and stir until completely dissolved to prepare a 10wt% polyvinyl alcohol aqueous solution.
[0115] After adding antioxidant 1010, add hydrochloric acid to adjust the pH to 3, then slowly add aldehyde mixture dropwise. After the addition is complete, heat to 30°C, keep the reaction at this temperature for 4 hours, and then add sodium hydroxide solution to neutralize the reaction system and terminate the reaction.
[0116] The neutralized reaction system was centrifuged, and the centrifuged product was washed multiple times with deionized water. After vacuum dehydration and drying at 60°C, the modified PVB resin was obtained.
[0117] The mass ratio of polyvinyl alcohol, antioxidant 1010, and aldehyde mixture is 100:0.3:60.
[0118] Detection method:
[0119] Chemical resistance test: The modified PVB resins prepared in Examples 1-7 and Comparative Examples 1-2 were mixed in a mass ratio of 75:15:1.5:5 for modified PVB resin, plasticizer, nano oxide and titanate coupling agent. The mixture was then extruded to prepare test film samples with a thickness of 5 mm. The samples were then immersed in salt solution and alkaline solution, respectively. After immersion for 12 h, 24 h and 48 h, respectively, the presence of swelling, cracking and sticky softening defects was tested.
[0120] Transmittance test: The modified PVB resins prepared in Examples 1-7 and Comparative Examples 1-2 were mixed in a mass ratio of 75:15:1.5:5 for modified PVB resin, plasticizer, nano oxide, and titanate coupling agent. The mixture was then extruded to prepare test film samples of 100mm×100mm×0.76mm. The samples were placed in an environment with a temperature of 23℃ and a relative humidity of 50% for 24 hours and then tested using a light transmittance meter with a light source wavelength of 550nm.
[0121] Haze detection: The modified PVB resins prepared in Examples 1-7 and Comparative Examples 1-2 were mixed in a mass ratio of 75:15:1.5:5 for modified PVB resin, plasticizer, nano oxide, and titanate coupling agent. The mixture was then extruded to prepare test film samples of 100mm×100mm×0.76mm. After standing for 24 hours in an environment with a temperature of 23℃ and a relative humidity of 50%, the haze was detected using a haze meter with a detection light source wavelength of 550nm.
[0122] UV irradiation resistance test: The modified PVB resins prepared in Examples 1-7 and Comparative Examples 1-2 were mixed in a mass ratio of 75:15:1.5:5 for modified PVB resin, plasticizer, nano-oxide, and titanate coupling agent. The mixture was then extruded to prepare test film samples of 100mm × 100mm × 0.76mm. These samples were placed in an environment of 23℃ and 50% relative humidity for 24 hours, and then placed in a UV irradiation chamber with a test light source wavelength of 340nm and an irradiation power of 0.7W / m². 2 The change in transmittance before and after irradiation was tested.
[0123] The test results are shown in Table 1 below.
[0124] Table 1. Performance testing of Examples 1-6 and Comparative Examples 1-2
[0125]
[0126] As can be seen from the data in the table above, a comparison of the data from Examples 1-3 and Examples 6 and 7 of the present invention shows that as the composition of each raw material component of the fluorinated acetal monoaldehyde derivative is gradually increased, the prepared fluorinated acetal monoaldehyde derivative can be better grafted onto the polyvinyl alcohol chain segment, thereby giving the PVB resin better salt and alkali resistance and radiation resistance. Furthermore, as can be seen from the data of Examples 1 and 4 in the table above, after increasing the amount of fluorinated acetal monoaldehyde derivative added, the salt and alkali resistance of the PVB film is further improved. In addition, due to the increase in fluorine content, the radiation resistance of the PVB resin is also greatly improved. The strong hydrophobicity and chemical inertness of fluorine can effectively block the penetration of oxygen and moisture, significantly reduce the oxidation rate of residual hydroxyl groups in PVB, inhibit yellowing from the source, and avoid a sharp drop in light transmittance.
[0127] As can be seen from the data of Examples 1 and 5, the radiation resistance of PVB resin was further improved by adding glyoxal. This is because the addition of glyoxal further intensifies the micro-crosslinking between linear segments of PVB, thereby improving the physical shielding effect of the resin material, reducing the erosion of external moisture and salt and alkali substances, and the micro-crosslinking also enhances the stability of the resin structure, which can effectively reduce the diffusion and transmission of free radicals, reduce the rate of degradation and deterioration, and thus sufficiently improve its radiation resistance.
[0128] As can be seen from the data of Comparative Example 1, without the introduction of fluorinated acetal monoaldehyde derivatives, the salt and alkali resistance of PVB resin decreased significantly. Furthermore, due to the lack of fluorine, the radiation resistance of PVB resin also decreased significantly, and the light transmittance decreased markedly. Comparative Example 2 shows that, without the addition of glyoxal micro-crosslinking, the salt and alkali resistance and radiation resistance of Comparative Example 2 decreased compared to Example 1.
[0129] Furthermore, it can be clearly seen from the data of Examples 1-7 of the present invention and Comparative Example 1 that, with the addition of the monomer containing fluorinated acetal monoaldehyde derivative, there was no strong negative impact on the transmittance and haze of the PVB resin. Its transmittance and haze are still within the qualified product standard and can be directly used in existing PVB film applications.
[0130] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A method for preparing a modified PVB resin, characterized in that, Includes the following steps: 2-Amino-1,3-propanediol was mixed with anhydrous methanol, then triethylamine and epifluoropropane were added. After heating and reacting, the solvent was removed by rotary evaporation to obtain a fluorinated propanediol derivative. The fluorinated propylene glycol derivative was mixed with anhydrous methanol, the pH was adjusted, and then glyoxal aqueous solution was added. After heating and reacting, sodium hydroxide was added to neutralize the mixture. The solvent was removed by rotary evaporation and the mixture was filtered to obtain the fluorinated acetal monoaldehyde derivative. A fluorinated acetal monoaldehyde derivative was mixed with n-butyraldehyde and glyoxal to obtain an aldehyde mixture. Polyvinyl alcohol (PVA) was mixed with deionized water to prepare an aqueous PVA solution. An antioxidant was added, the pH was adjusted, an aldehyde mixture was added, and the mixture was heated to react. Sodium hydroxide solution was added to neutralize the reaction system and terminate the reaction. The neutralized reaction system was centrifuged, and the centrifuged product was washed with deionized water and dried to obtain modified PVB resin.
2. The method for preparing a modified PVB resin according to claim 1, characterized in that: The mass ratio of 2-amino-1,3-propanediol, triethylamine, and epifluoropropane is 1:(0.06~0.11):(0.83~0.91).
3. The method for preparing a modified PVB resin according to claim 1, characterized in that: After adding triethylamine, the reaction system needs to be cooled to 0~10℃ before adding epifluoropropylene dropwise. During the heating reaction, the heating temperature is 30~45℃, and the stirring reaction time is 3~5h; After removing the solvent by rotary evaporation, the remaining product should be washed with deionized water at a temperature of 0~4℃ and then vacuum dried.
4. The method for preparing a modified PVB resin according to claim 1, characterized in that: The mass ratio of fluorinated propylene glycol derivatives to glyoxal is (3~3.1):
1.
5. The method for preparing a modified PVB resin according to claim 1, characterized in that: The substance used to adjust the pH value is hydrochloric acid, and the pH value is adjusted to 2~3; When adding glyoxal aqueous solution, the reaction system should be cooled to 0~10℃ before adding the glyoxal aqueous solution dropwise. During the heating reaction, the heating temperature is 25~35℃, and the stirring reaction time is 4~6h.
6. The method for preparing a modified PVB resin according to claim 1, characterized in that: The mass ratio of the fluorinated acetal monoaldehyde derivative to n-butyraldehyde and glyoxal is (1~2):(6.4~7):(0.04~0.08).
7. The method for preparing a modified PVB resin according to claim 1, characterized in that: The concentration of the polyvinyl alcohol aqueous solution is 10-15 wt%; the antioxidant is at least one of antioxidant 1010, antioxidant BHT and antioxidant 168.
8. The method for preparing a modified PVB resin according to claim 1, characterized in that: When adjusting the pH value, use hydrochloric acid to adjust the pH value of the reaction system to 1~3; During the heating reaction, the heating temperature is 30~50℃, and the reaction is stirred for 2~4 hours.
9. The method for preparing a modified PVB resin according to claim 1, characterized in that: The mass ratio of the polyvinyl alcohol, antioxidant, and aldehyde mixture is 100:(0.3~0.5):(60~70).
10. A modified PVB resin prepared by the preparation method according to any one of claims 1 to 9.