Ionic interlayer with complexed acidity and degree of neutralization and method of preparation

Abstract

This invention relates to the field of interlayer film technology in laminated glass, and more particularly to an ionic interlayer film and its preparation method that considers the acidity and neutralization degree of the composite. The resin component in the ionic interlayer film composite system is Na. + Type ethylene-methacrylic acid ionomer and Zn² + Ethylene-methacrylic acid ionomer; the total acidity of the ionic intermediate membrane composite system was 13.3~15.4 mgKOH / g, the total neutralization degree was 81.5%~83.5%, and the free carboxyl group content was 0.23~0.27 mmol / g; the total acidity, total neutralization degree, and free carboxyl group content were measured values; Zn²⁺ in the ionic intermediate membrane composite system + Concentration 0.8%~0.99%. This is determined by acidity, degree of neutralization, and Zn²⁺. + The synergistic balance of concentrations constructs an ordered phase structure of "hydrophobic microregions-ion clusters" at the molecular chain level, significantly inhibiting the diffusion path of water molecules while ensuring the reversible recovery of ionic bonds after boiling in water. After boiling in water at 100℃ for 16 hours, the adhesion retention rate of the product is ≥90%.

Description

Technical Field

[0001] This invention relates to the field of interlayer film technology in laminated glass, and more particularly to an ionic interlayer film and its preparation method that takes into account the acidity and neutralization of the composite. Background Technology

[0002] Ionic interlayers, with ethylene-methacrylic acid ionomers formed by partial neutralization of ethylene-methacrylic acid copolymer (EMAA) as their core substrate, have become a core functional material for high-end laminated glass due to their excellent transparency, penetration resistance, and interfacial adhesion. According to industry standards, the heat resistance safety index of ionic interlayers must pass a test of boiling in water at 100°C for 2 hours to 16 hours, after which the film structure must remain intact and the adhesion must not significantly decrease.

[0003] Currently, industry improvements to the performance of ionic interlayer membranes mainly focus on three areas: resin compound selection, additive optimization, and multilayer structure design. However, existing technologies generally suffer from performance bottlenecks: they exhibit sol-gel and degumming phenomena after being boiled in water at 100°C for less than 2 hours, and the adhesion retention rate is typically below 50%, failing to meet the long-term weather resistance and safety requirements of the high-end construction market.

[0004] Existing technologies for improving the performance of ionic intermediate membranes mainly focus on two directions: one is the treatment of Na+. + / Zn² + Fine-tuning the compounding ratio of ionomers can only slightly optimize mechanical properties, but it cannot break through the threshold of intermolecular forces, nor can it block the destruction of ionic bonds by water molecules, resulting in very limited improvement in boiling stability. The second approach is to improve interfacial adhesion by adding specific coupling agents, crosslinking agents, and other additives, but this approach is prone to causing system compatibility imbalance, leading to defects such as increased haze and the appearance of a paste-like substance, which in turn degrades the product's optical performance and processing stability. For example, Chinese patent application CN120986019A discloses a three-layer ionic intermediate membrane, which improves its water resistance through a co-extrusion structure of the intermediate and surface layers: the intermediate layer uses 20-50% of water-soluble Suryn resin A (Surlyn AE4500, PC2000, etc.) and 50-80% water-resistant Suryn resin B (Surlyn 8940, 8920, etc.) to reduce the proportion of easily soluble resin and improve water resistance; the surface layer incorporates 10-80% Kuraray Plus edge material, utilizing the high methacrylic acid content of the edge material to improve the impact value and surface hydrolysis resistance; at the same time, silane coupling agents, antioxidants, plasticizers, and other additives are added to further optimize performance. This scheme, through resin selection and multi-layer structure design, can meet the basic standard requirement of boiling at 100℃ for 2 hours, but still does not significantly improve water resistance. Summary of the Invention

[0005] The purpose of this invention is to propose an ionic intermediate membrane and its preparation method that takes into account the acidity and neutralization of the compound. The membrane achieves a water-resistant, boil-insoluble gel by regulating the acidity, neutralization and ionic catalytic activity of the ethylene-methacrylic acid ionomer compound.

[0006] To achieve this objective, the present invention adopts the following technical solution: An ionic intermediate membrane considering the acidity and neutralization degree of the compound, wherein the resin component in the ionic intermediate membrane compound system is Na. + Type ethylene-methacrylic acid ionomer and Zn² + Type ethylene-methacrylic acid ionomer; The Na + Type ethylene-methacrylic acid ionomer and Zn² + The acidity of the compounded ethylene-methacrylic acid ionomer was 13.3~15.4 mgKOH / g, the degree of neutralization was 81.5%~83.5%, and the free carboxyl group content was 0.23~0.27 mmol / g. The total acidity, total degree of neutralization, and free carboxyl group content were measured values. Total Zn²⁺ + The mass concentration is 0.8%~0.99%; the compound acidity, compound neutralization degree and free carboxyl content are measured values.

[0007] Furthermore, the Na + Type ethylene-methacrylic acid ionomer and the Zn² + The mass ratio of the ethylene-methacrylic acid ionomer is (0.8~1.25):(0.8~1.25).

[0008] Furthermore, the components of the ionic intermediate membrane complex system, by mass percentage, include: Na + Type ethylene-methacrylic acid ionomer: 44.5%~55%, Zn² + Ethylene-methacrylic acid ionomer: 44.5%~55%, epoxy coupling agent: 0.12%~0.18%, silane coupling agent: 0.045%~0.055%, alcohol plasticizer: 0.10%~0.12%, hindered phenolic antioxidant: 0.08%~0.12%, metal soap heat stabilizer: 0.10%~0.20%, benzotriazole ultraviolet absorber: 0.04%~0.06%; Among them, Na + Type ethylene-methacrylic acid ionomer and Zn² + The mass of the ethylene-methacrylic acid ionomer accounts for 99.2% to 99.5% of the total mass of the compound system.

[0009] Furthermore, the Na + Type ethylene-methacrylic acid ionomer and Zn²+ Free Zn²⁺ after compounding with ethylene-methacrylic acid ionomer + The mass concentration is less than 150 ppm.

[0010] Furthermore, when Na in the ionic intermediate membrane composite system + Type ethylene-methacrylic acid ionomer and Zn² + When the free carboxyl groups of the ethylene-methacrylic acid ionomer increase, the amount of epoxy coupling agent added should be reduced; When the Na + Type ethylene-methacrylic acid ionomer and Zn² + When the free carboxyl groups in the compounded ethylene-methacrylic acid ionomer are at a low level, a high addition amount of silane coupling agent is used; when the free carboxyl groups are at a high level, a low addition amount of silane coupling agent is used.

[0011] Furthermore, the Na + Type ethylene-methacrylic acid ionomer and Zn² + For every 0.01 mmol / g increase in the free carboxyl group content of the ethylene-methacrylic acid ionomer, the epoxy addition amount increases by a maximum of 0.01%.

[0012] A method for preparing an ionic intermediate membrane considering the acidity and neutralization of the compound, the method comprising the following steps: (1) Detect Na separately + Type ethylene-methacrylic acid ionomer and Zn² + The acid value, total carboxyl content, and metal ion content of the ethylene-methacrylic acid ionomer were used to calculate the blending ratio to achieve the desired blending acid value, degree of neutralization, and total Zn². + The mass concentration and free carboxyl group content fall within the target range; (2) Put Na + Type ethylene-methacrylic acid ionomer, Zn² + Ethylene-methacrylic acid ionomer, epoxy coupling agent, silane coupling agent, alcohol plasticizer, hindered phenolic antioxidant, metal soap heat stabilizer, and benzotriazole ultraviolet absorber are mixed evenly according to the specified ratio. (3) The mixture is added to the extruder and extruded and cast in a zoned gradient temperature control manner to obtain an ionic intermediate film.

[0013] Furthermore, in step (3), the extruder uses 8-zone heating, when the Na... + Type ethylene-methacrylic acid ionomer and Zn² + When the compound acid value of the ethylene-methacrylic acid ionomer increases, the temperature of zone 8 of the extruder should be reduced, with a larger decrease in the temperature of zones 4-6.

[0014] Furthermore, the temperature range of each zone of the extruder is as follows: feeding zone 1 145~150℃, compression zone 2 153~158℃, melting zone 3 160~165℃, mixing zone 4 163~169℃, zone 5 before primary vacuum 165~170℃, zone 6 before secondary vacuum 163~168℃, metering zone 7 162~167℃, and connecting zone 8 160~165℃; The extruder has a die temperature of 157~162℃, a screw speed of 240~260rpm, and a vacuum degree of ≥0.098MPa.

[0015] Furthermore, in step (1), when Na is detected... + Type ethylene-methacrylic acid ionomer or Zn² + When the acid value of the ethylene-methacrylic acid ionomer is greater than 15.4 mgKOH / g, the mixture of the ethylene-methacrylic acid ionomer with the high acid value and the ethylene-methacrylic acid ionomer with the low acid value is calculated using the following formula: ,

[0016] Where m1 and m2 are the masses of different batches of ethylene-methacrylic acid ionomer, respectively, and AV1 and AV2 are the measured average acid values ​​of different batches of ethylene-methacrylic acid ionomer, respectively. 目标 The target is the compound acid value.

[0017] The technical solution provided by this invention may include the following beneficial effects: This invention utilizes acidity, neutralization degree, and Zn²⁺. + The synergistic balance of concentrations constructs an ordered phase structure of "hydrophobic microregions-ion clusters" at the molecular chain level, significantly inhibiting water molecule diffusion paths while ensuring reversible recovery of ionic bonds after boiling. After boiling at 100℃ for 16 hours, the product retains ≥90% of its adhesion. This compound system achieves a triple balance between epoxy reactivity, ionic crosslinking strength, and side reaction suppression, ensuring sufficient interfacial reaction sites while avoiding side reactions such as silane self-polymerization and excessive epoxy crosslinking. The product, with a thickness of 5.0 mm, exhibits a haze ≤2.27%, impact adhesion ≥7, tensile strength ≥40 MPa, and fully meets the standards for optical properties, mechanical properties, weather resistance, and processing stability. Detailed Implementation

[0018] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the present invention.

[0019] Existing technologies have not recognized the relationship between the free carboxyl group content, the hydrolytic stability of the ionic crosslinking network, and Zn² in the compound system of ethylene-methacrylic acid ionomer (trade name: sarin ionomer or sarin resin). + The quantitative synergistic relationship among the three catalytic activities has been limited to crude adjustments of surface formulations and processes, thus failing to overcome the industry bottleneck of water boiling performance. This invention provides an ionic intermediate membrane that considers the acidity and neutralization degree of the compounded system, by synergistically influencing the free carboxyl group content, ionic crosslinking network stability, and Zn²⁺ content of the resin compounding system. + Catalytic activity improves the product's resistance to boiling water.

[0020] An embodiment of the present invention provides an ionic intermediate membrane considering the acidity and neutralization degree of the compound, wherein the resin component in the ionic intermediate membrane compound system is Na. + Type ethylene-methacrylic acid ionomer and Zn² + Type ethylene-methacrylic acid ionomer; The Na + Type ethylene-methacrylic acid ionomer and Zn² + The compound acidity of the ethylene-methacrylic acid ionomer is 13.3~15.4 mgKOH / g, the degree of neutralization is 81.5%~83.5%, the free carboxyl group content is 0.23~0.27 mmol / g, and the total Zn²⁺ content is [not specified]. + The mass concentration is 0.8%~0.99%; the acidity, neutralization degree and free carboxyl content of the compound are the measured values ​​of the compound system.

[0021] The free carboxyl group content (acidity) in the compound system determines the upper limit of active sites in the epoxy reaction. Controlling the free carboxyl group content between 0.23 and 0.27 mmol / g ensures interfacial adhesion while preventing phase separation. The degree of neutralization determines the hydrolytic stability of the ionic crosslinking network. Controlling it between 81.5% and 83.5% allows for reversible recovery of ionic bonds after boiling in water. Zn² + The concentration simultaneously regulates the epoxy reaction conversion rate and the risk of silane self-polymerization, and can be controlled at 0.8%~0.99%, which can suppress side reactions while ensuring sufficient reaction.

[0022] The unique properties of ethylene-methacrylic acid ionomers (high transparency, high toughness, and good heat-sealing properties) derive entirely from their ionic crosslinking network. Metal ions form reversible ionic bonds with carboxyl groups, which dissociate at high temperatures, imparting good processing fluidity to the resin. At room temperature, the ionic crosslinks reform, giving the resin excellent mechanical properties and elasticity. Na... + The high density of ionic crosslinks formed gives the resin good transparency and toughness. Zn² +The resulting ionic bonds have higher bond energies, giving the resin better thermal stability and water resistance. The synergistic effect of the two metal ions gives the ionic crosslinked network both high strength and high elasticity. Zn² + Simultaneously catalyzing the formation and hydrolysis of ester bonds, there is an optimal concentration range of 0.8%-0.99%. Within this concentration range, the hydrolysis rate of ester bonds in the compound system is the lowest, and the ester bond retention rate is >90% after boiling for 16 hours. The degree of neutralization is the core determinant of the strength of the ionic crosslinking network. Within the neutralization range of 75%-88%, each 1% increase increases the tensile strength by 0.4-0.6 MPa. When the neutralization degree is >88%, the increase in tensile strength tends to plateau, and the elongation at break begins to decrease. When the neutralization degree is <75%, the ionic crosslinking density is too low, and the resin becomes a viscous fluid, unusable. This scheme limits the neutralization degree to 81.5%~83.5%.

[0023] It should be noted that Na + Type / Zn² + Ethylene-methacrylic acid ionomers refer to ionomer resins obtained by partially neutralizing ethylene-methacrylic acid copolymer (EMAA) with sodium and zinc ions, respectively. Their acidity originates from unneutralized free carboxyl groups (-COOH). The degree of neutralization refers to the molar percentage of carboxyl groups neutralized by metal ions out of the total carboxyl groups. The acid value is not the "pure free carboxyl group" directly calculated by those skilled in the art, but rather all acidic sites that can be neutralized by KOH, including: completely free -COOH, and weakly bound monodentate coordination ion pairs (-COO). - …M⁺, which can dissociate under titration pH conditions. Zn² + In the system, the single-tooth coordinated -COO - …Zn⁺ still retains reactivity, Zn² + The number of reactive sites in ethylene-methacrylic acid ionomers is greater than the number of completely free -COOH groups. Zn² + Because of its higher binding constant, it preferentially occupies carboxyl sites, resulting in a slightly lower measured acid value and a slightly higher measured degree of neutralization than the theoretical value. Therefore, in this invention, the compound acid value refers to the total acid value measured by titration after mixing the two ionomers in the compound system, expressed in mgKOH / g; the compound neutralization degree refers to the molar percentage of carboxyl groups neutralized by metal ions in the compound system, expressed as a measured value; the free carboxyl content refers to the molar content of carboxyl groups in the compound system that have not formed ionic bonds and can participate in chemical reactions, expressed in mmol / g; and the free Zn²⁺ content... + This refers to zinc ions that have not formed a coordinate bond with a carboxyl group and can be detected by solvent extraction, measured in ppm.

[0024] Preferably, the Na + Type ethylene-methacrylic acid ionomer and the Zn² +The mass ratio of the ethylene-methacrylic acid ionomer is (0.8~1.25):(0.8~1.25). When Na + The ratio is higher than 1.25, Zn² + Below 0.8, the acid value and free carboxyl groups will exceed the upper limit, Zn² + Insufficient concentration; when Zn² + The ratio is higher than 1.25, Na + Below 0.8, the acid value and free carboxyl groups will fall below the lower limit, Zn² + Concentration exceeded the standard. Na + The UV aging rate of ionomers is Zn² + A ratio of 2.3 times that of Zn²⁺, or approximately 1:1, can keep the yellowing index within a reasonable range; at the same time, avoid Zn²⁺. + An excessively high proportion of Zn² leads to increased melt viscosity and a narrower processing window. + Zn² in type ethylene-methacrylic acid ionomer + It is a natural Lewis acid catalyst for the reaction of epoxy and carboxyl groups, and also a catalyst for silane self-polymerization. In the complex system, Zn²⁺ + While improving the hydrolysis resistance of ionic bonds, it catalyzes the hydrolysis of ester bonds. When the two resins are blended in a ratio of approximately 1:1, Zn² + The concentration effectively catalyzes the reaction between epoxy and carboxyl groups without causing severe silane self-polymerization. The average degree of neutralization ensures sufficient ionic crosslinking strength while retaining enough free carboxyl groups for interfacial reactions.

[0025] More preferably, the components of the ionic intermediate membrane complex system, by mass percentage, include: Na + Type ethylene-methacrylic acid ionomer: 44.5%~55%, Zn² + Ethylene-methacrylic acid ionomer: 44.5%~55%, epoxy coupling agent: 0.12%~0.18%, silane coupling agent: 0.045%~0.055%, alcohol plasticizer: 0.10%~0.12%, hindered phenolic antioxidant: 0.08%~0.12%, metal soap heat stabilizer: 0.10%~0.20%, benzotriazole ultraviolet absorber: 0.04%~0.06%; Among them, Na + Type ethylene-methacrylic acid ionomer and Zn² + The mass of the ethylene-methacrylic acid ionomer accounts for 99.2% to 99.5% of the total mass of the compound system.

[0026] The ionic intermediate membrane compound system comprises a main resin and six types of functional additives, with the dosage range of each additive matched to the core acidity parameter. The dosage of epoxy coupling agents is matched to the molar content of free carboxyl groups to ensure sufficient reaction without over-discharge; silane coupling agents are strictly controlled within an extremely low range to avoid free Zn²⁺. + Catalyzed self-polymerization; the remaining additives are general-purpose functional additives, and the dosage range takes into account both functional realization and system compatibility.

[0027] The reaction equation for epoxy coupling agents is: In the compound system, the free carboxyl groups are the only active sites for the epoxy reaction. Higher acidity results in a greater amount of reactive epoxy and better adhesion. Lower neutralization leads to more free carboxyl groups and a faster reaction rate; however, excessively low neutralization can cause a decrease in the strength of the ionic crosslinking network. Zn² + As a Lewis acid catalyst, it can reduce the reaction activation energy by about 40% and increase the conversion rate from 30% to over 90%. Its catalytic cycle is as follows: Zn²⁺ + Coordination with the oxygen atom of the epoxy group causes electronic polarization of the epoxy three-membered ring, reducing the bond energy of the CO bond within the ring and significantly enhancing the epoxy reactivity. The free carboxyl groups on the ethylene-methacrylic acid ionomer molecular chain dissociate, transferring hydrogen protons to the polarized epoxy oxygen atom, promoting ring opening of the epoxy ring and forming a carbocation intermediate. The carboxylate anion generated by the carboxyl group dissociation acts as a nucleophile, attacking the aforementioned carbocation intermediate and undergoing a nucleophilic addition reaction to form an ester bond structure with a secondary hydroxyl group, achieving covalent bonding between the epoxy coupling agent and the resin molecular chain. After the reaction is complete, Zn²⁺ + The product structure is dissociated, restoring catalytic activity, allowing it to participate in the next catalytic reaction between epoxide and carboxyl groups, thus achieving cyclic catalysis. This scheme limits the amount of epoxide added to 0.12%~0.18%; if it exceeds 0.2%, the epoxide will undergo self-polymerization.

[0028] The haze of the ionic interlayer in laminated glass is mainly determined by the phase separation size. A phase separation size <50nm results in a haze <1.5%, invisible to the naked eye; a phase separation size of 50-200nm results in a haze of 1.5%-3.0%, slight haze; and a phase separation size >200nm results in a haze >3.0%, noticeably white. Lower acidity in the compound leads to lower solubility of the epoxy additives, making phase separation more likely and increasing haze. Higher carboxyl content and resin refractive index result in smaller differences in refractive indices between the resin and epoxy additives, leading to lower haze. Higher acidity increases the risk of silane self-polymerization and epoxy crosslinking, and the resulting nanoparticles contribute to increased haze. In this compound system, the epoxy coupling agent has high solubility and fewest by-products. The epoxy additive phase separation size is approximately 30nm, far below the visible light wavelength, resulting in low haze.

[0029] The higher the degree of neutralization, the more stable the ionic cross-linking network, and the less easily it is destroyed during boiling. The higher the acidity, the more complete the epoxy reaction, the stronger the interfacial bonding, and the higher the retention rate of adhesion after boiling. Zn² + The ionic bonds formed are far more resistant to hydrolysis than those formed by Na. + Therefore, Zn² + A higher proportion of ionomers results in better water boiling performance. Water boiling performance of the compound system: the ion-crosslinked network undergoes only slight dissociation during boiling and fully recovers upon cooling. During boiling, not only does the ion-crosslinked network dissociate, but the ester bonds formed between the epoxy and carboxyl groups also hydrolyze. Zn² + It simultaneously catalyzes the formation and hydrolysis of ester bonds, with an optimal concentration range (0.8%-1.0%). In the compound system, the ester bond hydrolysis rate is the lowest, and the ester bond retention rate is >90% after boiling for 16 hours.

[0030] Free Zn² + A concentration of 150 ppm is the critical value for silane self-polymerization. In the embodiments of this invention, Na... + Type ethylene-methacrylic acid ionomer and Zn² + Free Zn²⁺ after compounding with ethylene-methacrylic acid ionomer + The mass concentration is less than 150 ppm.

[0031] Based on the above formulation amount, preferably, when the Na + Type ethylene-methacrylic acid ionomer and Zn² + When the free carboxyl groups increase after compounding with type ethylene-methacrylic acid ionomer, the amount of epoxy coupling agent added should be reduced; When Na + Type ethylene-methacrylic acid ionomer and Zn² + When the free carboxyl groups in the compounded ethylene-methacrylic acid ionomer are at a low level, a high addition amount of silane coupling agent is used; when the free carboxyl groups are at a high level, a low addition amount of silane coupling agent is used.

[0032] More preferably, the Na + Type ethylene-methacrylic acid ionomer and Zn² + For every 0.01 mmol / g increase in the free carboxyl group content of the ethylene-methacrylic acid ionomer, the epoxy addition amount increases by a maximum of 0.01%.

[0033] As an example, when the compound acid value is 13.0~13.4 mgKOH / g, the amount of epoxy coupling agent added is 0.17%, and the amount of silane coupling agent added is 0.055%. When the compound acid value is 13.5~13.8 mgKOH / g, the amount of epoxy coupling agent added is 0.16%, and the amount of silane coupling agent added is 0.055%. When the compound acid value is 13.9~14.5 mgKOH / g, the amount of epoxy coupling agent added is 0.15%, and the amount of silane coupling agent added is 0.055%. When the compound acid value is 14.6~14.9 mgKOH / g, the amount of epoxy coupling agent added is 0.14%, and the amount of silane coupling agent added is 0.050%. When the compound acid value is 15.0~15.4 mgKOH / g, the amount of epoxy coupling agent added is 0.13% and the amount of silane coupling agent added is 0.050%.

[0034] As an example, epoxy coupling agents react with free carboxyl groups to form covalent bonds, thereby improving interfacial adhesion. They are selected from one or more of the following: glycidyl tert-carbonate (Cardura E10P), epichlorohydrin (ECH), bisphenol A type epoxy resin (E-51), ethylene glycol diglycidyl ether (AGE), and ADEKA EP-4080E. Silane coupling agents improve the interfacial compatibility between resin and glass, and are selected from one or more of γ-glycidoxypropyltrimethoxysilane (OFS-6040 / KH-560), 3-glycidoxypropyltriethoxysilane (KH-561 / A-1871), γ-methacryloyloxypropyltrimethoxysilane (KH-570 / A-174), γ-aminopropyltriethoxysilane (KH-550 / A-1100), and vinyltriethoxysilane (A-151). Alcohol plasticizers are used to adjust melt flowability and promote the dispersion of additives. They are selected from one or more of DEHCH, dipropylene glycol (DPG), tripropylene glycol (TPG), 1,4-butanediol (BDO), and ethylene glycol monobutyl ether (EB). Hindered phenolic antioxidants are used to inhibit the high-temperature oxidative degradation of resins and are selected from one or more of the following: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (1010), N,N'-bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (Irganox 1098), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (1076), 2,6-di-tert-butyl-p-cresol (BHT), and B225 hindered phenolic + phosphite binary composite antioxidants. The benzotriazole ultraviolet absorber is selected from one or more of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV-P), 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole (UV327), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (UV326), and 2-hydroxy-4-n-octyloxybenzophenone (UV531); Metal soap-based heat stabilizers are used to inhibit high-temperature degradation of resins and improve processing stability. They are selected from one or more of the following: calcium stearate / zinc stearate complex (CaSt2 / ZnSt2, mass ratio 1:1~3:1), barium stearate / zinc stearate complex, and calcium-zinc composite stabilizers.

[0035] Accordingly, the present invention also provides a method for preparing an ionic intermediate membrane considering the acidity and neutralization of the compound, for preparing the above-mentioned ionic intermediate membrane considering the acidity and neutralization of the compound, the preparation method comprising the following steps: (1) Detect Na separately + Type ethylene-methacrylic acid ionomer and Zn² + The acid value, total carboxyl content, and metal ion content of the ethylene-methacrylic acid ionomer were used to calculate the blending ratio to achieve the average acid value, average degree of neutralization, and Zn² of the blended system. + The concentration and free carboxyl group content fall within the target range; (2) Put Na + Type ethylene-methacrylic acid ionomer, Zn² + Ethylene-methacrylic acid ionomer, epoxy coupling agent, silane coupling agent, alcohol plasticizer, hindered phenolic antioxidant, metal soap heat stabilizer, and benzotriazole ultraviolet absorber are mixed evenly according to the specified ratio. (3) The mixture is added to the extruder and extruded and cast in a zoned gradient temperature control manner to obtain an ionic intermediate film.

[0036] The preparation method of this invention requires first testing the acid value, total carboxyl group, and metal ion content of the single resin, and then calculating the compounding ratio to ensure that the total acidity, total neutralization, and free carboxyl group content of the compounding system are within the specified range, thereby obtaining a high-quality ionic intermediate membrane.

[0037] Preferably, in step (3), the extruder uses an 8-zone heating system when the Na... + Type ethylene-methacrylic acid ionomer and Zn² +When the acid value of the compound ethylene-methacrylic acid ionomer increases, the temperature of zone 8 of the extruder is reduced, with the largest reduction observed in zones 4-6. A linkage rule between extrusion temperature and acid value was established: the higher the acid value, the stronger the reactivity of the epoxy and silane, and the faster the side reaction rate; therefore, the temperature needs to be lowered to suppress the side reactions. Conversely, a lower acid value requires raising the temperature to promote the reaction. Zones 4-6 are the main reaction zones of the extruder, where epoxy esterification and silane self-polymerization mainly occur; therefore, the temperature adjustment range is the largest in these zones.

[0038] Specifically, the temperature range of each zone of the extruder is as follows: feeding zone 1 145~150℃, compression zone 2 153~158℃, melting zone 3 160~165℃, mixing zone 4 163~169℃, zone 5 before primary vacuum 165~170℃, zone 6 before secondary vacuum 163~168℃, metering zone 7 162~167℃, and connecting zone 8 160~165℃; The extruder has a die temperature of 157~162℃, a screw speed of 240~260rpm, and a vacuum degree of ≥0.098MPa.

[0039] Among them, the first vacuum section and the second vacuum section are the heating sections upstream of the first vacuum exhaust port and the second vacuum exhaust port, respectively. The material first passes through these sections and then enters the corresponding vacuum exhaust port.

[0040] Zones 1-3 (feeding-melting) involve resin melting and initial dispersion. Temperature primarily affects the molten state and has a relatively small impact on the reaction. The corresponding acid value adjustment range is ±1-2℃. Zones 4-6 (mixing-reaction) are the additive dispersion and main reaction zones. Epoxy esterification and silane self-polymerization mainly occur in this area, making it the core area for adjustment. The corresponding acid value adjustment range is ±2-3℃. Zones 7-8 and the mold (metering-forming) involve melt homogenization and forming. Temperature primarily affects melt viscosity and flowability. The corresponding acid value adjustment range is ±1-2℃.

[0041] As an example, in step (3), the temperature of the extruder reaction zone is adjusted according to the acid value of the compound system: When the compound acid value is 13.0~13.4 mgKOH / g, the temperature in zone 5 is 168~169℃; When the compound acid value is 13.5~13.8 mgKOH / g, the temperature in zone 5 is 167~168℃; When the compound acid value is 13.9~14.5mgKOH / g, the temperature in zone 5 is 166~168℃; When the compound acid value is 14.6~14.9 mgKOH / g, the temperature in zone 5 is 166~167℃; When the acid value of the compound is 15.0~15.4 mgKOH / g, the temperature in zone 5 is 165℃.

[0042] In step (1), when Na is detected... + Type ethylene-methacrylic acid ionomer or Zn² + When the acid value of the ethylene-methacrylic acid ionomer is greater than 15.4 mgKOH / g, the mixture of the ethylene-methacrylic acid ionomer with the high acid value and the ethylene-methacrylic acid ionomer with the low acid value is calculated using the following formula: ,

[0043] Where m1 and m2 are the masses of different batches of ethylene-methacrylic acid ionomer, respectively, and AV1 and AV2 are the measured average acid values ​​of different batches of ethylene-methacrylic acid ionomer, respectively. 目标 The target is the compound acid value.

[0044] Each batch of raw materials is tested for acid value, total carboxyl content, and metal ion content. The average value of each parameter is calculated. If the data of the same batch of materials fluctuates greatly, the raw materials need to be mixed and then re-formulated. If the acid value exceeds 15.4 mg KOH / g, batches with high and low acid values ​​need to be mixed to reduce production costs and reduce raw material waste.

[0045] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed according to conventional methods and conditions or according to the product instructions. Unless otherwise specified, the reagents are commercially available; and the performance of products from different sources does not have a significant impact.

[0046] Example 1

[0047] The ionic intermediate membrane in this embodiment has the following compounding system by mass percentage: Na + Type ethylene-methacrylic acid ionomer 49.7%, Zn² + The composition includes: 49.7% ethylene-methacrylic acid ionomer, 0.150% epoxy coupling agent (bisphenol A type epoxy resin (E-51)), 0.055% silane coupling agent (γ-glycidyl etheroxypropyltrimethoxysilane OFS-6040), 0.110% alcohol plasticizer (tripropylene glycol TPG), 0.1% hindered phenolic antioxidant (antioxidant 1010), 0.1% metal soap heat stabilizer (calcium stearate / zinc stearate mass ratio 2:1 compound), and 0.045% benzotriazole ultraviolet absorber (UV326).

[0048] Na + Type ethylene-methacrylic acid ionomer and Zn² + Zn² after compounding with ethylene-methacrylic acid ionomer + Mass concentration 0.9%, free Zn²⁺+ The mass concentration is 120 ppm, the acidity of the compound is 14.2 mg KOH / g, the degree of neutralization of the compound is 82.5%, and the content of free carboxyl groups is 0.253 mmol / g.

[0049] The method for preparing the ionic intermediate membrane in this embodiment includes the following steps: (1) Detect Na separately + Type ethylene-methacrylic acid ionomer and Zn² + The acid value, total carboxyl content, and metal ion content of the ethylene-methacrylic acid ionomer were used to calculate the blending ratio to achieve the average acid value, average degree of neutralization, and Zn² of the blended system. + The concentration and free carboxyl group content fall within the target range; (2) Put Na + Type ethylene-methacrylic acid ionomer, Zn² + Ethylene-methacrylic acid ionomer, epoxy coupling agent, silane coupling agent, alcohol plasticizer, hindered phenolic antioxidant, metal soap heat stabilizer, and benzotriazole ultraviolet absorber are mixed evenly according to the specified ratio. (3) The mixture is added to the extruder and extruded and cast in a zoned gradient temperature control manner to obtain an ionic intermediate film. The temperature range of each zone of the extruder is: Zone 1 148℃, Zone 2 156℃, Zone 3 163℃, Zone 4 166℃, Zone 5 168℃, Zone 6 166℃, Zone 7 165℃, Zone 8 163℃, die temperature 160℃, screw speed 250rpm, and system vacuum degree 0.098MPa.

[0050] Example 2

[0051] The ionic intermediate membrane in this embodiment has the following compounding system by mass percentage: Na + Type ethylene-methacrylic acid ionomer: 55.0%, Zn² + Ethylene-methacrylic acid ionomer: 44.5%, epoxy coupling agent (bisphenol A type epoxy resin (E-51)): 0.120%, silane coupling agent (OFS-6040): 0.045%, alcohol plasticizer (tripropylene glycol TPG): 0.1%, hindered phenolic antioxidant (antioxidant 1010): 0.080%, metal soap heat stabilizer (calcium stearate / zinc stearate 2:1 compound): 0.1%, benzotriazole ultraviolet absorber (UV326): 0.055%.

[0052] Na + Type ethylene-methacrylic acid ionomer and Zn² + Zn² after compounding with ethylene-methacrylic acid ionomer +Mass concentration 0.8%, free Zn²⁺ + The mass concentration is 105 ppm, the acidity of the compound is 15.4 mg KOH / g, the neutralization degree of the compound is 81.5%, and the free carboxyl content is 0.27 mmol / g.

[0053] The method for preparing the ionic intermediate membrane in this embodiment includes the following steps: (1) Detect Na separately + Type ethylene-methacrylic acid ionomer and Zn² + The acid value, total carboxyl content, and metal ion content of the ethylene-methacrylic acid ionomer were used to calculate the blending ratio to achieve the average acid value, average degree of neutralization, and Zn² of the blended system. + The concentration and free carboxyl group content fall within the target range; (2) Put Na + Type ethylene-methacrylic acid ionomer, Zn² + Ethylene-methacrylic acid ionomer, epoxy coupling agent, silane coupling agent, alcohol plasticizer, hindered phenolic antioxidant, metal soap heat stabilizer, and benzotriazole ultraviolet absorber are mixed evenly according to the specified ratio. (3) The mixture is added to the extruder and extruded and cast in a zoned gradient temperature control manner to obtain an ionic intermediate film. The temperature range of each zone of the extruder is: Zone 1 145℃, Zone 2 153℃, Zone 3 160℃, Zone 4 163℃, Zone 5 165℃, Zone 6 163℃, Zone 7 162℃, Zone 8 160℃, Die temperature: 157℃, Screw speed: 240rpm, Vacuum degree: 0.099MPa.

[0054] Example 3

[0055] The ionic intermediate membrane in this embodiment has the following compounding system by mass percentage: Na + Type ethylene-methacrylic acid ionomer: 44.5%, Zn² + Ethylene-methacrylic acid ionomer: 54.765%, epoxy coupling agent (bisphenol A type epoxy resin (E-51)): 0.180%, silane coupling agent (OFS-6040): 0.055%, alcohol plasticizer (tripropylene glycol TPG): 0.120%, hindered phenolic antioxidant (antioxidant 1010): 0.120%, metal soap heat stabilizer (calcium stearate / zinc stearate 2:1 compound): 0.2%, benzotriazole ultraviolet absorber (UV326): 0.060%.

[0056] Na + Type ethylene-methacrylic acid ionomer and Zn² + Zn² after compounding with ethylene-methacrylic acid ionomer +Mass concentration 0.8%, free Zn²⁺ + The mass concentration is 132 ppm, the acidity of the compound is 13.3 mg KOH / g, the degree of neutralization of the compound is 83.5%, and the content of free carboxyl groups is 0.23 mmol / g.

[0057] The method for preparing the ionic intermediate membrane in this embodiment includes the following steps: (1) Detect Na separately + Type ethylene-methacrylic acid ionomer and Zn² + The acid value, total carboxyl content, and metal ion content of the ethylene-methacrylic acid ionomer were used to calculate the blending ratio to achieve the average acid value, average degree of neutralization, and Zn² of the blended system. + The concentration and free carboxyl group content fall within the target range; (2) Put Na + Type ethylene-methacrylic acid ionomer, Zn² + Ethylene-methacrylic acid ionomer, epoxy coupling agent, silane coupling agent, alcohol plasticizer, hindered phenolic antioxidant, metal soap heat stabilizer, and benzotriazole ultraviolet absorber are mixed evenly according to the specified ratio. (3) The mixture is added to an extruder and extruded and cast in a zoned gradient temperature control manner to obtain an ionic intermediate film. The temperature range of each zone of the extruder is: Zone 1 150℃, Zone 2 158℃, Zone 3 165℃, Zone 4 169℃, Zone 5 170℃, Zone 6 168℃, Zone 7 167℃, Zone 8 165℃, Die temperature: 162℃, Screw speed: 260rpm, System vacuum degree: 0.099MPa.

[0058] Example 4

[0059] The ionic intermediate membrane in this embodiment has the following compounding system by mass percentage: Na + Type ethylene-methacrylic acid ionomer: 49.99%, Zn² + Ethylene-methacrylic acid ionomer: 49.5%, epoxy coupling agent (bisphenol A type epoxy resin (E-51)): 0.140%, silane coupling agent (OFS-6040): 0.05%, alcohol plasticizer (tripropylene glycol TPG): 0.1%, hindered phenolic antioxidant (antioxidant 1010): 0.080%, metal soap heat stabilizer (calcium stearate / zinc stearate 2:1 compound): 0.1%, benzotriazole ultraviolet absorber (UV326): 0.04%.

[0060] Na + Type ethylene-methacrylic acid ionomer and Zn² + Zn² after compounding with ethylene-methacrylic acid ionomer +Mass concentration 0.89%, free Zn²⁺ + The mass concentration is 118 ppm, the acidity of the compound is 14.3 mg KOH / g, the degree of neutralization of the compound is 82.3%, and the content of free carboxyl groups is 0.255 mmol / g.

[0061] The method for preparing the ionic intermediate membrane in this embodiment includes the following steps: (1) Detect Na separately + Type ethylene-methacrylic acid ionomer and Zn² + The acid value, total carboxyl content, and metal ion content of the ethylene-methacrylic acid ionomer were used to calculate the blending ratio to achieve the average acid value, average degree of neutralization, and Zn² of the blended system. + The concentration and free carboxyl group content fall within the target range; (2) Put Na + Type ethylene-methacrylic acid ionomer, Zn² + Ethylene-methacrylic acid ionomer, epoxy coupling agent, silane coupling agent, alcohol plasticizer, hindered phenolic antioxidant, metal soap heat stabilizer, and benzotriazole ultraviolet absorber are mixed evenly according to the specified ratio. (3) The mixture is added to the extruder and extruded and cast in a gradient temperature controlled manner in different zones to obtain an ionic intermediate film. The temperature range of each zone of the extruder is: Zone 1 148℃, Zone 2 156℃, Zone 3 163℃, Zone 4 166℃, Zone 5 168℃, Zone 6 166℃, Zone 7 165℃, Zone 8 163℃, Die temperature: 160℃, Screw speed: 250rpm, System vacuum degree: 0.098MPa.

[0062] Example 5

[0063] The ionic intermediate membrane in this embodiment has the following compounding system by mass percentage: Na + Type ethylene-methacrylic acid ionomer: 49.625%, Zn² + Ethylene-methacrylic acid ionomer: 49.665%, epoxy coupling agent (bisphenol A type epoxy resin (E-51)): 0.155%, silane coupling agent (OFS-6040): 0.055%, alcohol plasticizer (tripropylene glycol TPG): 0.120%, hindered phenolic antioxidant (antioxidant 1010): 0.120%, metal soap heat stabilizer (calcium stearate / zinc stearate 2:1 compound): 0.2%, benzotriazole ultraviolet absorber (UV326): 0.060%.

[0064] Na + Type ethylene-methacrylic acid ionomer and Zn² + Zn² after compounding with ethylene-methacrylic acid ionomer+ Mass concentration 0.87%, free Zn²⁺ + The mass concentration is 122 ppm, the acidity of the compound is 14.1 mg KOH / g, the degree of neutralization of the compound is 82.6%, and the content of free carboxyl groups is 0.251 mmol / g.

[0065] The method for preparing the ionic intermediate membrane in this embodiment includes the following steps: (1) Detect Na separately + Type ethylene-methacrylic acid ionomer and Zn² + The acid value, total carboxyl content, and metal ion content of the ethylene-methacrylic acid ionomer were used to calculate the blending ratio to achieve the average acid value, average degree of neutralization, and Zn² of the blended system. + The concentration and free carboxyl group content fall within the target range; (2) Put Na + Type ethylene-methacrylic acid ionomer, Zn² + Ethylene-methacrylic acid ionomer, epoxy coupling agent, silane coupling agent, alcohol plasticizer, hindered phenolic antioxidant, metal soap heat stabilizer, and benzotriazole ultraviolet absorber are mixed evenly according to the specified ratio. (3) The mixture is added to the extruder and extruded and cast in a zoned gradient temperature control manner to obtain an ionic intermediate film. The temperature range of each zone of the extruder is: Zone 1 147℃, Zone 2 155℃, Zone 3 162℃, Zone 4 165℃, Zone 5 167℃, Zone 6 165℃, Zone 7 164℃, Zone 8 162℃, Die temperature: 159℃, Screw speed: 250rpm, System vacuum degree: 0.098MPa.

[0066] Example 6

[0067] The ionic intermediate membrane in this embodiment has the following compounding system by mass percentage: Na + Type ethylene-methacrylic acid ionomer: 45.315%, Zn² + Ethylene-methacrylic acid ionomer: 54.04%, Epoxy coupling agent (bisphenol A type epoxy resin (E-51)): 0.170%, Silane coupling agent (OFS-6040): 0.055%, Alcohol plasticizer (tripropylene glycol TPG): 0.110%, Hindered phenolic antioxidant (antioxidant 1010): 0.1%, Metal soap heat stabilizer (calcium stearate / zinc stearate 2:1 compound): 0.150%, Benzotriazole ultraviolet absorber (UV326): 0.060%.

[0068] Na + Type ethylene-methacrylic acid ionomer and Zn² +Zn² after compounding with ethylene-methacrylic acid ionomer + Mass concentration 0.98%, free Zn²⁺ + The mass concentration is 130 ppm, the acidity of the compound is 13.4 mg KOH / g, the degree of neutralization of the compound is 82.4%, and the content of free carboxyl groups is 0.232 mmol / g.

[0069] The method for preparing the ionic intermediate membrane in this embodiment includes the following steps: (1) Detect Na separately + Type ethylene-methacrylic acid ionomer and Zn² + The acid value, total carboxyl content, and metal ion content of the ethylene-methacrylic acid ionomer were used to calculate the blending ratio to achieve the average acid value, average degree of neutralization, and Zn² of the blended system. + The concentration and free carboxyl group content fall within the target range; (2) Put Na + Type ethylene-methacrylic acid ionomer, Zn² + Ethylene-methacrylic acid ionomer, epoxy coupling agent, silane coupling agent, alcohol plasticizer, hindered phenolic antioxidant, metal soap heat stabilizer, and benzotriazole ultraviolet absorber are mixed evenly according to the specified ratio. (3) The mixture is added to the extruder and extruded and cast in a zoned gradient temperature control manner to obtain an ionic intermediate film. The temperature range of each zone of the extruder is: Zone 1 149℃, Zone 2 157℃, Zone 3 164℃, Zone 4 168℃, Zone 5 169℃, Zone 6 167℃, Zone 7 166℃, Zone 8 164℃, Die temperature: 161℃, Screw speed: 255rpm, System vacuum degree: 0.099MPa.

[0070] Example 7

[0071] The ionic intermediate membrane in this embodiment has the following compounding system by mass percentage: Na + Type ethylene-methacrylic acid ionomer: 49.690%, Zn² + Ethylene-methacrylic acid ionomer: 49.690%, epoxy coupling agent (ethylene glycol diglycidyl ether AGE): 0.150%, silane coupling agent (γ-aminopropyltriethoxysilane KH-550): 0.050%, alcohol plasticizer (tripropylene glycol TPG): 0.110%, hindered phenolic antioxidant (Irganox 1098): 0.1%, metal soap heat stabilizer (commercial calcium-zinc composite stabilizer): 0.150%, benzotriazole ultraviolet absorber (UV-P): 0.060%.

[0072] Na + Type ethylene-methacrylic acid ionomer and Zn²+ Zn² after compounding with ethylene-methacrylic acid ionomer + Mass concentration 0.9%, free Zn²⁺ + The mass concentration was 119 ppm, the acidity of the compound was 14.2 mg KOH / g, the neutralization degree of the compound was 82.4%, and the free carboxyl content was 0.252 mmol / g.

[0073] The method for preparing the ionic intermediate membrane in this embodiment includes the following steps: (1) Detect Na separately + Type ethylene-methacrylic acid ionomer and Zn² + The acid value, total carboxyl content, and metal ion content of the ethylene-methacrylic acid ionomer were used to calculate the blending ratio to achieve the average acid value, average degree of neutralization, and Zn² of the blended system. + The concentration and free carboxyl group content fall within the target range; (2) Put Na + Type ethylene-methacrylic acid ionomer, Zn² + Ethylene-methacrylic acid ionomer, epoxy coupling agent, silane coupling agent, alcohol plasticizer, hindered phenolic antioxidant, metal soap heat stabilizer, and benzotriazole ultraviolet absorber are mixed evenly according to the specified ratio. (3) The mixture is added to the extruder and extruded and cast in a gradient temperature controlled manner in different zones to obtain an ionic intermediate film. The temperature range of each zone of the extruder is: Zone 1 148℃, Zone 2 156℃, Zone 3 163℃, Zone 4 166℃, Zone 5 168℃, Zone 6 166℃, Zone 7 165℃, Zone 8 163℃, Die temperature: 160℃, Screw speed: 250rpm, System vacuum degree: 0.098MPa.

[0074] Comparative Example 1 The ionic intermediate membrane in this comparative example has the following compound system by mass percentage: Na + Type Ionomer of ethylene-methacrylic acid: 40.0%, Zn² + Ethylene-methacrylic acid ionomer: 59.4%, epoxy coupling agent (bisphenol A type epoxy resin (E-51)): 0.150%, silane coupling agent (OFS-6040): 0.055%, alcohol plasticizer (tripropylene glycol TPG): 0.110%, hindered phenolic antioxidant (antioxidant 1010): 0.1%, metal soap heat stabilizer (calcium stearate / zinc stearate 2:1 compound): 0.140%, benzotriazole ultraviolet absorber (UV326): 0.045%.

[0075] Na + Type ethylene-methacrylic acid ionomer and Zn² +Zn² after compounding with ethylene-methacrylic acid ionomer + Mass concentration 1.3%, compound acid value: 12.8 mg KOH / g, compound neutralization degree: 84.1%, free carboxyl content: 0.22 mmol / g, free Zn²⁺ + Mass concentration: 165 ppm. The preparation steps of the intermediate membrane in this comparative example are the same as those in Example 1.

[0076] Comparative Example 2 The ionic intermediate membrane in this comparative example has the following compound system by mass percentage: Na + Type ethylene-methacrylic acid ionomer: 55.0%, Zn² + Ethylene-methacrylic acid ionomer: 44.5%, epoxy coupling agent (bisphenol A type epoxy resin (E-51)): 0.120%, silane coupling agent (OFS-6040): 0.045%, alcohol plasticizer (tripropylene glycol TPG): 0.1%, hindered phenolic antioxidant (antioxidant 1010): 0.080%, metal soap heat stabilizer (calcium stearate / zinc stearate 2:1 compound): 0.1%, benzotriazole ultraviolet absorber (UV326): 0.055%.

[0077] Na + Type ethylene-methacrylic acid ionomer and Zn² + The blended acid value of the ethylene-methacrylic acid ionomer was 15.8 mg KOH / g, the degree of neutralization was 80.8%, the free carboxyl group content was 0.28 mmol / g, and the total Zn² content was [not specified]. + Mass concentration: 0.55%, free Zn²⁺ + Mass concentration: 82 ppm. The preparation steps of the intermediate membrane in this comparative example are the same as those in Example 2.

[0078] Comparative Example 3 The ionic intermediate membrane in this comparative example has the following compound system by mass percentage: Na + Type Ionomer of ethylene-methacrylic acid: 43.0%, Zn² + Ethylene-methacrylic acid ionomer: 56.320%, epoxy coupling agent (bisphenol A type epoxy resin (E-51)): 0.150%, silane coupling agent (OFS-6040): 0.080%, alcohol plasticizer (tripropylene glycol TPG): 0.110%, hindered phenolic antioxidant (antioxidant 1010): 0.1%, metal soap heat stabilizer (calcium stearate / zinc stearate 2:1 compound): 0.2%, benzotriazole ultraviolet absorber (UV326): 0.040%.

[0079] Na +Type ethylene-methacrylic acid ionomer and Zn² + The blended acid value of the ethylene-methacrylic acid ionomer was 13.1 mgKOH / g, the degree of neutralization was 83.8%, the free carboxyl group content was 0.225 mmol / g, and the total Zn² content was [not specified]. + Mass concentration 1.35%, free Zn² + The mass concentration was 172 ppm. The preparation steps of the intermediate membrane in this comparative example were the same as those in Example 1.

[0080] All performance parameters in the embodiments and comparative examples of this invention were tested using the following uniform method: 1. Acid value and free carboxyl groups of the compound: determined by potentiometric titration with potassium hydroxide-ethanol standard solution, in accordance with GB / T 2895-2008; 2. Neutralization degree of the compound: Calculated by the total carboxyl content (acid-base titration + elemental analysis correction) and the content of bound metal ions (ICP-OES), i.e., neutralization degree = (molar amount of bound carboxyl groups / molar amount of total carboxyl groups) × 100%; 3. Total Zn² in the compound system + Concentration: Measured using ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry). 4. Free Zn²⁺ in the complex system + Concentration: The zinc content in the extract was determined by ICP-OES after Soxhlet extraction with anhydrous ethanol for 24 h.

[0081] The intermediate films obtained in Examples 1-7 and Comparative Examples 1-3 were tested. Test methods: Adhesion retention rate after boiling: The laminated glass sample was boiled in 100℃ boiling water for 16 hours; Impact adhesion: Test the impact adhesion according to GB / T 32021-2015, and calculate the adhesion grade retention rate before and after boiling in water; Haze: Tested using a 5.0 mm thick laminated glass sample, in accordance with GB / T 2410-2008; Tensile strength: Tested according to GB / T 1040.3.

[0082] The test results are shown in the table below.

[0083]

[0084] Results analysis:

[0085] Examples 1-7 showed adhesion retention rates of ≥90% after 16 hours of boiling in water, haze of ≤2.27% at 5.0 mm, and tap adhesion of ≥7, fully meeting performance targets. The closer the parameters are to the center of the range (e.g., Example 1), the better the overall performance, conforming to the normal distribution law of material properties. Example 7 used aminosilane instead of epoxysilane. Due to the higher reactivity of amino and carboxyl groups, trace amounts of cross-linked particles were generated, resulting in slightly higher haze than the baseline Example 1, but still meeting performance requirements, demonstrating the universality of this solution for different types of additives.

[0086] In Comparative Example 1, Zn² + When the concentration and degree of neutralization exceed the upper limit, excessive ionic cross-linking and free zinc catalyze the hydrolysis of ester bonds result in a significant decrease in adhesion after boiling, along with the appearance of a slight paste-like substance, verifying the effects of Zn²⁺. + The necessity of concentration windows. In Comparative Example 2, the acid value exceeded the upper limit, and the degree of neutralization was related to Zn². + When the concentration is below the lower limit, the ionic cross-linked network has insufficient resistance to hydrolysis, resulting in significant edge degumming after boiling, with an adhesion retention rate of only 63%, verifying the core role of acidity and neutralization control. In Comparative Example 3, the silane dosage exceeded the standard, and the free zinc exceeded the critical value, causing silane to self-polymerize into a large number of nanoparticles, and the haze soared to 3.32%. At the same time, the boiling performance deteriorated simultaneously, verifying the rationality of the silane dosage and the critical value of free zinc.

[0087] In summary, this invention utilizes acidity, neutralization degree, and Zn²⁺. + The quantitative synergy of the three concentrations, combined with the dynamic matching of additive dosage and extrusion process, has achieved a breakthrough improvement in the water resistance of ionic intermediate films, while also taking into account optical performance and processing stability.

[0088] Other components and operations of the ionic intermediate membrane considering the compound acidity and neutralization degree according to embodiments of the present invention and its preparation method are known to those skilled in the art and will not be described in detail here. When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. The described performance can be achieved within the proportions range of the present invention. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by those skilled in the art to which this invention pertains.

[0089] Although embodiments of the invention have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.

Claims

1. An ionic intermediate membrane considering the acidity and neutralization degree of a compound, characterized in that, The resin component in the ionic intermediate membrane composite system is Na. + Type ethylene-methacrylic acid ionomer and Zn² + Type ethylene-methacrylic acid ionomer; The Na + Type ethylene-methacrylic acid ionomer and Zn² + The compound acidity of the ethylene-methacrylic acid ionomer is 13.3~15.4 mgKOH / g, the degree of neutralization is 81.5%~83.5%, the free carboxyl group content is 0.23~0.27 mmol / g, and the total Zn²⁺ content is [not specified]. + The mass concentration is 0.8%~0.99%; the compound acidity, compound neutralization degree and free carboxyl content are measured values.

2. The ionic intermediate membrane according to claim 1, characterized in that, The Na + Type ethylene-methacrylic acid ionomer and the Zn² + The mass ratio of the ethylene-methacrylic acid ionomer is (0.8~1.25):(0.8~1.25).

3. The ionic intermediate membrane according to claim 1 or 2, characterized in that, The components of the ionic intermediate membrane complex system, by mass percentage, include: Na + Type ethylene-methacrylic acid ionomer: 44.5%~55%, Zn² + Ethylene-methacrylic acid ionomer: 44.5%~55%, epoxy coupling agent: 0.12%~0.18%, silane coupling agent: 0.045%~0.055%, alcohol plasticizer: 0.10%~0.12%, hindered phenolic antioxidant: 0.08%~0.12%, metal soap heat stabilizer: 0.10%~0.20%, benzotriazole ultraviolet absorber: 0.04%~0.06%; Among them, Na + The combined mass of the type ethylene-methacrylic acid ionomer and the Zn²+ type ethylene-methacrylic acid ionomer accounts for 99.2% to 99.5% of the total mass of the compound system.

4. The ionic intermediate membrane according to claim 3, characterized in that, The Na + Type ethylene-methacrylic acid ionomer and Zn² + Free Zn²⁺ after compounding with ethylene-methacrylic acid ionomer + The mass concentration is less than 150 ppm.

5. The ionic intermediate membrane according to claim 3, characterized in that, When the Na + Type ethylene-methacrylic acid ionomer and Zn² + When the free carboxyl groups increase after compounding with type ethylene-methacrylic acid ionomer, the amount of epoxy coupling agent added should be reduced; When the Na + Type ethylene-methacrylic acid ionomer and Zn² + When the free carboxyl groups in the compounded ethylene-methacrylic acid ionomer are at a low level, a high addition amount of silane coupling agent is used; when the free carboxyl groups are at a high level, a low addition amount of silane coupling agent is used.

6. The ionic intermediate membrane according to claim 5, characterized in that, The Na + Type ethylene-methacrylic acid ionomer and Zn² + For every 0.01 mmol / g increase in the free carboxyl group content of the ethylene-methacrylic acid ionomer, the epoxy addition amount increases by a maximum of 0.01%.

7. A method for preparing an ionic intermediate membrane considering the acidity and neutralization degree of the compound, characterized in that, The method for preparing the ionic intermediate membrane according to claims 3-6, considering the acidity and neutralization of the compound, comprises the following steps: (1) Detect Na separately + Type ethylene-methacrylic acid ionomer and Zn² + The acid value, total carboxyl content, and metal ion content of the ethylene-methacrylic acid ionomer were used to calculate the blending ratio to achieve the desired blending acid value, degree of neutralization, and total Zn². + The mass concentration and free carboxyl group content fall within the target range; (2) Put Na + Type ethylene-methacrylic acid ionomer, Zn² + Ethylene-methacrylic acid ionomer, epoxy coupling agent, silane coupling agent, alcohol plasticizer, hindered phenolic antioxidant, metal soap heat stabilizer, and benzotriazole ultraviolet absorber are mixed evenly according to the specified ratio. (3) The mixture is added to the extruder and extruded and cast in a zoned gradient temperature control manner to obtain an ionic intermediate film.

8. The preparation method according to claim 7, characterized in that, In step (3), the extruder uses an 8-zone heating system. When the Na... + Type ethylene-methacrylic acid ionomer and Zn² + When the compound acid value of the ethylene-methacrylic acid ionomer increases, the temperature of zone 8 of the extruder should be reduced, with a larger decrease in the temperature of zones 4-6.

9. The preparation method according to claim 8, characterized in that, The temperature range of each zone of the extruder is as follows: feeding zone 1 145~150℃, compression zone 2 153~158℃, melting zone 3 160~165℃, mixing zone 4 163~169℃, zone 5 before primary vacuum 165~170℃, zone 6 before secondary vacuum 163~168℃, metering zone 7 162~167℃, and connecting zone 8 160~165℃. The extruder has a die temperature of 157~162℃, a screw speed of 240~260rpm, and a vacuum degree of ≥0.098MPa.

10. The preparation method according to claim 7, characterized in that, In step (1), when Na is detected... + Type ethylene-methacrylic acid ionomer or Zn² + When the acid value of the ethylene-methacrylic acid ionomer is greater than 15.4 mgKOH / g, the mixture of the ethylene-methacrylic acid ionomer with the high acid value and the ethylene-methacrylic acid ionomer with the low acid value is calculated using the following formula: , Where m1 and m2 are the masses of different batches of ethylene-methacrylic acid ionomer, respectively, and AV1 and AV2 are the measured average acid values ​​of different batches of ethylene-methacrylic acid ionomer, respectively. 目标 The target is the acid value of the compound.

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