A multi-ketone cross-linked polyvinyl butyral resin and a method for preparing the same

Abstract

The present application provides a kind of polyketone crosslinking polyvinyl butyral resin and its preparation method, wherein a kind of polyketone crosslinking polyvinyl butyral resin contains diketone group, ester group, ether group and hydroxyl functional group, is obtained by the reaction of two types of polyketone crosslinking agent and PVA;Another polyketone crosslinking polyvinyl butyral resin contains triketone group, ester group and hydroxyl functional group, which is obtained by the reaction of three types of polyketone crosslinking agent and PVA.Compared with the PVB transparent film made of only ordinary PVB, its light transmittance, haze and adhesion are greatly improved, the present application polyvinyl butyral resin crosslinking degree is high, and the reaction is mild and controllable.

Description

Technical Field

[0001] This invention patent relates to the synthesis of polymer materials, specifically a polyketone-crosslinked polyvinyl butyral resin and its preparation method. Background Technology

[0002] Polyvinyl butyral (PVB) is a polymer material produced by the acetalization reaction of polyvinyl alcohol (PVA) and n-butyral under acidic conditions. Its molecular structure retains hydroxyl groups, acetal groups, and a small amount of acetyl groups, exhibiting excellent adhesion, high transparency, toughness, weather resistance, and film-forming properties. It is currently a core material in the fields of laminated safety glass, photovoltaic encapsulation, high-end adhesives, and coatings. As early as the mid-20th century, PVB had already achieved industrial applications. With its outstanding impact resistance, penetration resistance, sound insulation, heat insulation, and UV blocking properties, it quickly became the preferred material for interlayer films in automotive, architectural, and aerospace safety glass. In the photovoltaic industry, PVB, with its advantages of aging resistance, high insulation, high light transmittance, and stable adhesion, has become a high-performance encapsulation material to replace traditional EVA. In addition, PVB is also widely used in ceramic decals, aluminum foil, textile treatment, anti-corrosion coatings, and structural adhesives.

[0003] Currently, industrial PVB resin is mainly produced using the precipitation method. By controlling the emulsification, condensation, neutralization, washing, and drying processes, the resin's acetal degree, hydroxyl content, viscosity, and particle morphology can be adjusted. To further improve strength, heat resistance, and dimensional stability, the industry commonly employs cross-linking modification technology. Common cross-linking systems include polyfunctional aldehydes, diesters, carboxyl self-crosslinking, and organosilicon / nano-intercalation crosslinking, which can significantly improve the molecular weight, mechanical properties, and solvent resistance of PVB, enabling it to meet the stringent requirements of high-end safety glass, photovoltaic modules, and functional films.

[0004] Currently, the industry has conducted extensive research and development on crosslinking systems and supporting processes. Patents US4696971, CN200510015706.6, and CN201210494116.6 optimize emulsifiers and emulsion defoaming systems to reduce reaction residues and small molecule precipitation, improving the stability of the crosslinking process and thus enhancing the light transmittance and adhesion performance of PVB. Patent CN200910114882.3 uses organic nano-montmorillonite combined with plasticizers for modification, improving the tensile strength and heat resistance of PVB sheets while crosslinking. Patent CN200910219935.8 uses rosin... The synergistic effect of components such as alcohol-soluble phenolic resin enhances the bonding strength of PVB. Patents CN201110311068.8, CN201110312110.8, and CN201110442018.3 respectively introduce nano-weather-resistant additives, polyethylene glycol viscoelastic materials, and ultraviolet absorbers, enabling PVB to possess weather resistance, sound insulation, and photovoltaic applicability characteristics on the basis of crosslinking modification. Patent CN201510959533.7 improves the interfacial adhesion between crosslinked PVB film and glass by adding a bonding strength regulator. However, the above methods only optimize the crosslinking effect to a limited extent from the aspects of emulsion system and functional additives, and the strength improvement of PVB is not significant, and cannot fundamentally solve the problem of poor mechanical strength and bonding strength of PVB film. To address this, researchers have shifted their focus to regulating the crosslinking agent and acetalization reagent system. They have employed multifunctional polyaldehyde compounds for crosslinking to increase the molecular weight of PVB and thus enhance its strength. Patents CN202211614943.4 and US 4902464A use dialdehyde and polyaldehyde compounds as crosslinking agents to improve the degree of acetalization through intermolecular crosslinking, thereby enhancing the adhesive and mechanical properties of PVB.

[0005]

[0006] Patent US 4950714A uses formaldehyde to partially replace butyraldehyde in the reaction, improving the acetal uniformity and surface adhesion of PVB. Patent US 6835784B2 adds oxalate diesters as mild crosslinking aids to work with butyraldehyde to complete the acetal reaction, effectively improving acetal uniformity, reducing melt index, and enhancing mechanical properties. However, multi-aldehyde crosslinking agents, represented by dialdehyde, still have significant drawbacks: these crosslinking agents have high activity, poor selectivity, and excessively fast reaction rates, leading to uneven crosslinking and poor product quality reproducibility; the excessively fast crosslinking rate causes large PVB particles to form rapidly, preventing sufficient condensation of hydroxyl groups within the particles; at the same time, uneven crosslinking further leads to uneven distribution of plasticizers, ultimately causing fluctuations in film strength and adhesion strength, and deteriorating particle size uniformity and optical properties. Summary of the Invention

[0007] The technical problem to be solved by this invention is to provide a polyketone-based crosslinked polyvinyl butyral resin and its preparation method. The ketone-based crosslinking agent, due to its increased steric hindrance, exhibits a moderate rate of acetalization reaction with the hydroxyl groups of PVA, enabling mild and controllable crosslinking speed, significantly improving the uniformity of resin powder particle size and the reproducibility of product quality. The crosslinking agent contains two or more ketone functional groups, which can effectively reduce the resin melt index and significantly improve the bonding strength and mechanical properties of PVB. Furthermore, the crosslinking agent contains both ester and hydroxyl groups, which provides better compatibility with plasticizers and significantly improves the optical properties of the film.

[0008] To address the aforementioned technical problems, embodiments of the present invention provide a polyketone-crosslinked polyvinyl butyral resin having the structure shown in formula (I):

[0009]

[0010] Wherein, R1 is a straight-chain alkyl group with 1-2 carbon atoms, and R2 is an alkyl group with 2-6 carbon atoms or a polyethylene glycol group with a degree of polymerization of 2-3.

[0011] x, y, z, and m are all integers, with x ranging from 200 to 2500 and y ranging from 20 to 400; the values ​​of z and m are related to the degree of acetalization.

[0012] Specifically, R2 is -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2- or -CH2CH2OCH2CH2-, -CH2CH2OCH2CH2OCH2CH2-.

[0013] The raw materials for preparing polyketone crosslinked polyvinyl butyral resin include PVA, type II polyketone crosslinking agent, emulsifier, acid catalyst and butyral.

[0014] Preferably, the type II polyketone crosslinking agent is one of ethylene glycol diacetate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol diacetate, butanediol diacetate, butanediol diacetate, neopentyl glycol diacetate, neopentyl glycol diacetate, hexanediol diacetate, hexanediol diacetate, diethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, and triethylene glycol diacetate.

[0015] Preferably, the emulsifier is one or more of sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfonate (AES).

[0016] Preferably, the acid catalyst is one or more of hydrochloric acid, sulfuric acid, and phosphoric acid.

[0017] Preferably, the PVA is selected with a degree of polymerization of 300-2400 and a degree of alcoholysis of 85-99.9 mol%.

[0018] This invention also provides a method for preparing polyketide crosslinked polyvinyl butyral resin, comprising the following steps:

[0019] S1.1 Prepare PVA into an aqueous solution, then add emulsifier and acid catalyst at room temperature and stir until homogeneous to obtain PVA reaction solution;

[0020] S1.2 Mix butyraldehyde and type II polyketide crosslinking agent evenly, then slowly add them dropwise to the PVA reaction solution, heat to the reaction temperature, and continue to react at this temperature for a period of time;

[0021] S1.3. Then, slowly add alkali solution to adjust the reaction solution to alkalinity to stop the reaction. Wash the product with deionized water, centrifuge, dry to constant weight and then pulverize to finally obtain polyketone crosslinked polyvinyl butyral resin.

[0022] In step S1.1, the concentration of the PVA aqueous solution is 1-15%; the degree of polymerization of the polyvinyl alcohol is 300-2400, and the degree of hydrolysis is 85-99.9 mol%; the emulsifier is one or more of sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfonate (AES); and the acid catalyst is one or more of hydrochloric acid, sulfuric acid, and phosphoric acid.

[0023] In step S1.2, the type II polyketone crosslinking agent is one of ethylene glycol diacetate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol diacetate, butanediol diacetate, butanediol diacetate, neopentyl glycol diacetate, neopentyl glycol diacetate, hexanediol diacetate, hexanediol diacetate, diethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, and triethylene glycol diacetate.

[0024] In step S1.3, the pH value at the time of termination is 7-8.

[0025] The present invention also provides a polyketone-crosslinked polyvinyl butyral resin having the formula ( The structure shown is as follows:

[0026]

[0027] Where n is 3, R1 is a straight-chain alkyl group with 1-2 carbon atoms, and R3 is CH3 or OH.

[0028] x, y, z, and m are all integers, with x ranging from 200 to 2500 and y ranging from 20 to 400; the values ​​of z and m are related to the degree of acetalization.

[0029] The raw materials for preparing polyketone crosslinked polyvinyl butyral resin include PVA, type III polyketone crosslinking agent, emulsifier, acid catalyst and butyral.

[0030] Preferably, the type III polyketide crosslinking agent is one or more of trihydroxypropane triacetyl acetate, trihydroxypropane triacetylpropionate, pentaerythritol triacetyl acetate, and pentaerythritol triacetylpropionate.

[0031] Preferably, the emulsifier is one or more of sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfonate (AES).

[0032] Preferably, the acid catalyst is one or more of hydrochloric acid, sulfuric acid, and phosphoric acid.

[0033] Preferably, the PVA is selected from PVA with a degree of polymerization of 300-2400 and a degree of hydrolysis of 85-99.9 mol%.

[0034] This invention also provides a method for preparing polyketide crosslinked polyvinyl butyral resin, comprising the following steps:

[0035] S2.1 Prepare PVA into an aqueous solution, then add emulsifier and acid catalyst at room temperature and stir until homogeneous to obtain PVA reaction solution;

[0036] S2.2 Mix butyraldehyde and tri-type polyketide crosslinking agent evenly, then slowly add them dropwise to the PVA reaction solution, heat to the reaction temperature, and continue to react at this temperature for a period of time;

[0037] S2.3. Then, slowly add alkali solution to adjust the reaction solution to alkalinity to stop the reaction. Wash the product with deionized water, centrifuge, dry to constant weight and then pulverize to finally obtain polyketone crosslinked polyvinyl butyral resin.

[0038] In step S2.1, the concentration of the PVA aqueous solution is 1-15%; the degree of polymerization of the polyvinyl alcohol is 300-2400, and the degree of hydrolysis is 85-99.9 mol%; the emulsifier is one of sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfonate (AES); and the acid catalyst is one or more of hydrochloric acid, sulfuric acid, and phosphoric acid.

[0039] In step S2.2, the type III polyketide crosslinking agent is one or more of trihydroxypropane triacetyl acetate, trihydroxypropane triacetylpropionate, pentaerythritol triacetyl acetate, and pentaerythritol triacetylpropionate.

[0040] In step S2.3, the pH value at the time of termination is 7-8.

[0041] The beneficial effects of the above-described technical solution of the present invention are as follows:

[0042] 1. In this invention, the prepared structure is as shown in the formula ( The polyketone crosslinked polyvinyl butyral resin shown contains diketone, ester, ether, and hydroxyl functional groups, and is prepared as shown in the structural formula ( The polyketone-crosslinked polyvinyl butyral resin shown contains triketone, ester, and hydroxyl functional groups. Compared to ordinary polyvinyl butyral resin made solely from butyraldehyde, its compatibility with plasticizers, crosslinking uniformity, and optical properties of the prepared film are significantly improved.

[0043] 2. In this invention, during the preparation of polyketone-crosslinked polyvinyl butyral resin, the intermediate contains a ketone crosslinking structure that is milder than the aldehyde group, enabling a mild and controllable crosslinking rate and significantly improving the uniformity of resin powder particle size and reaction reproducibility. The crosslinking agent contains two or more ketone functional groups, which can effectively reduce the resin melt index and significantly improve the bonding strength and mechanical properties of PVB. Therefore, the polyketone-crosslinked polyvinyl butyral resin prepared by this invention has high bonding strength, good particle size uniformity, and the preparation method is simple, highly repeatable, and the production process is mild and controllable. Attached Figure Description

[0044] Figure 1 The ethylene glycol diacetylpropionate in Example 1 of this invention 1 H NMR spectrum;

[0045] Figure 2 The infrared spectrum of polyketone crosslinked PVB resin powder 1# in Example 1 of the present invention is shown. Detailed Implementation

[0046] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with specific embodiments.

[0047] This invention provides a polyketone-crosslinked polyvinyl butyral resin having the structure shown in formula (I):

[0048]

[0049] Wherein, R1 is a straight-chain alkyl group with 1-2 carbon atoms, and R2 is an alkyl group with 2-6 carbon atoms or a polyethylene glycol group with a degree of polymerization of 2-3.

[0050] x, y, z, and m are all integers, with x ranging from 200 to 2500 and y ranging from 20 to 400; the values ​​of z and m are related to the degree of acetalization.

[0051] The raw materials for preparing polyketone crosslinked polyvinyl butyral resin include PVA, type II polyketone crosslinking agent, emulsifier, acid catalyst and butyral.

[0052] Preferably, the type II polyketone crosslinking agent is one of ethylene glycol diacetate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol diacetate, butanediol diacetate, butanediol diacetate, neopentyl glycol diacetate, neopentyl glycol diacetate, hexanediol diacetate, hexanediol diacetate, diethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, and triethylene glycol diacetate.

[0053] Preferably, the emulsifier is one or more of sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfonate (AES).

[0054] Preferably, the acid catalyst is one or more of hydrochloric acid, sulfuric acid, and phosphoric acid.

[0055] Preferably, the PVA is selected from PVA with a degree of polymerization of 300-2400 and a degree of hydrolysis of 85-99.9 mol%.

[0056] This invention also provides a method for preparing polyketide crosslinked polyvinyl butyral resin, comprising the following steps:

[0057] S1.1 PVA is prepared into an aqueous solution, then an emulsifier and an acid catalyst are added at room temperature and stirred until homogeneous to obtain the PVA reaction solution. In this step, the concentration of the PVA aqueous solution is 1-15%; the degree of polymerization of polyvinyl alcohol is 300-2400, and the degree of alcoholysis is 85-99.9 mol%; the emulsifier is one of sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfonate (AES); the acid catalyst is one or more of hydrochloric acid, sulfuric acid, and phosphoric acid. The detailed steps of step S1.1 are as follows:

[0058] PVA and deionized water were added to a beaker, stirred, and heated above 90°C until completely dissolved, then cooled to room temperature. Next, an emulsifier and acid catalyst were added, and the mixture was stirred to obtain the PVA reaction solution.

[0059] The concentration of the PVA aqueous solution is 1-15%, preferably 10%.

[0060] The emulsifiers include, but are not limited to, sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfonate (AES), with sodium dodecylbenzene sulfonate (SDBS) being preferred.

[0061] The acid catalyst includes, but is not limited to, hydrochloric acid, sulfuric acid, and phosphoric acid, with hydrochloric acid being preferred.

[0062] The heating temperature is above 90℃, preferably 90-100℃.

[0063] The mass ratio of PVA to emulsifier is 1:0.02-1:0.06, preferably 1:0.04.

[0064] The mass ratio of PVA to acid catalyst is 1:0.01-1:0.1, preferably 1:0.03.

[0065] S1.2. Mix butyraldehyde and type II polyketone crosslinking agent evenly, then slowly add the mixture dropwise to the PVA reaction solution. Heat to the reaction temperature and continue the reaction at this temperature for a period of time. In this step, the type II polyketone crosslinking agent is one of the following: ethylene glycol diacetate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol diacetate, butylene glycol diacetate, butylene glycol diacetate, neopentyl glycol diacetate, neopentyl glycol diacetate, hexanediol diacetate, hexanediol diacetate, diethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, and triethylene glycol diacetate. The detailed steps of step S1.2 are as follows:

[0066] Butyraldehyde was added to a type II polyketide crosslinking agent to prepare a mixed solution, which was then added dropwise to the PVA reaction solution under continuous stirring. The temperature was slowly raised to 70°C, and the reaction was carried out for 4 hours to obtain a polyketide crosslinked polyvinyl butyral product, as shown in formula ( As shown in the figure.

[0067]

[0068] The reaction equation is as follows:

[0069]

[0070] Wherein, R1 is a straight-chain alkyl group with 1-2 carbon atoms, and R2 is an alkyl group with 2-6 carbon atoms or a polyethylene glycol group with a degree of polymerization of 2-3.

[0071] x, y, z, and m are all integers, with x ranging from 200 to 2500 and y ranging from 20 to 400; the values ​​of z and m are related to the degree of acetalization.

[0072] The degree of polymerization of the raw material PVA is 300-2400, and the degree of alcoholysis is 85-99.9 mol%. Preferably, the degree of polymerization is 500-2000, and the degree of alcoholysis is 95-99 mol%.

[0073] The type II polyketone crosslinking agent is ethylene glycol diacetate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol diacetate, butanediol diacetate, butanediol diacetate, neopentyl glycol diacetate, neopentyl glycol diacetate, hexanediol diacetate, hexanediol diacetate, diethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, triethylene glycol diacetate, preferably ethylene glycol diacetate.

[0074] The reaction time is 4 hours.

[0075] The reaction temperature is between 20-100℃, preferably 70℃.

[0076] The mass ratio of PVA to butyraldehyde is 1:0.1-1:0.5, preferably 1:0.3.

[0077] The mass ratio of PVA to type II polyketone crosslinking agent is 1:0.05-1:0.2, preferably 1:0.1.

[0078] The equipment used is a container equipped with heating and stirring, and various mixers, reaction vessels, and other equipment can be used.

[0079] S1.3 Then, slowly add alkali solution to adjust the reaction solution to alkalinity to stop the reaction. Wash the product with deionized water, centrifuge, dry to constant weight, and then pulverize to finally obtain polyketide-crosslinked polyvinyl butyral resin. In this step, the pH value at the time of termination is 7-8. The detailed steps of step S1.3 are as follows:

[0080] After the reaction is complete, alkali solution is slowly added to the reaction solution to adjust the pH to 7-8 to stop the reaction. The product is washed with deionized water, centrifuged, dried for several hours to constant weight, and then pulverized to obtain polyketide crosslinked PVB resin powder.

[0081] The alkali may be any one or more combinations of sodium hydroxide, potassium hydroxide, potassium carbonate, or sodium carbonate, preferably sodium hydroxide.

[0082] In the washing process of the product, deionized water is used as the washing solvent.

[0083] The drying process of the product is carried out at a temperature of 40-60℃ and a drying time of 1-6 hours, with the preferred drying temperature being 50℃ and the preferred drying time being 4 hours.

[0084] The present invention also provides a polyketone-crosslinked polyvinyl butyral resin having the formula ( The structure shown is as follows:

[0085]

[0086] Where n is 3, R1 is a straight-chain alkyl group with 1-2 carbon atoms, and R3 is CH3 or OH.

[0087] x, y, z, and m are all integers, with x ranging from 200 to 2500 and y ranging from 20 to 400; the values ​​of z and m are related to the degree of acetalization.

[0088] The raw materials for preparing polyketone crosslinked polyvinyl butyral resin include PVA, type III polyketone crosslinking agent, emulsifier, acid catalyst and butyral.

[0089] Preferably, the type III polyketide crosslinking agent is one or more of trihydroxypropane triacetyl acetate, trihydroxypropane triacetylpropionate, pentaerythritol triacetyl acetate, and pentaerythritol triacetylpropionate.

[0090] Preferably, the emulsifier is one or more of sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfonate (AES).

[0091] Preferably, the acid catalyst is one or more of hydrochloric acid, sulfuric acid, and phosphoric acid.

[0092] Preferably, the PVA is selected from PVA with a degree of polymerization of 300-2400 and a degree of hydrolysis of 85-99.9 mol%.

[0093] This invention also provides a method for preparing polyketide crosslinked polyvinyl butyral resin, comprising the following steps:

[0094] S2.1 PVA is prepared into an aqueous solution, then an emulsifier and an acid catalyst are added at room temperature and stirred until homogeneous to obtain the PVA reaction solution. In this step, the concentration of the PVA aqueous solution is 1-15%; the degree of polymerization of polyvinyl alcohol is 300-2400, and the degree of alcoholysis is 85-99.9 mol%; the emulsifier is one or more of sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfonate (AES); the acid catalyst is one or more of hydrochloric acid, sulfuric acid, and phosphoric acid. The detailed steps of step S2.1 are as follows:

[0095] PVA and deionized water were added to a beaker, stirred, and heated above 90°C until completely dissolved, then cooled to room temperature. Next, an emulsifier and acid catalyst were added, and the mixture was stirred to obtain the PVA reaction solution.

[0096] The concentration of the PVA aqueous solution is 1-15%, preferably 10%.

[0097] The emulsifiers include, but are not limited to, sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfonate (AES), with sodium dodecylbenzene sulfonate (SDBS) being preferred.

[0098] The acid catalyst includes, but is not limited to, hydrochloric acid, sulfuric acid, and phosphoric acid, with hydrochloric acid being preferred.

[0099] The heating temperature is above 90℃, preferably 90-100℃.

[0100] The mass ratio of PVA to emulsifier is 1:0.02-1:0.06, preferably 1:0.04.

[0101] The mass ratio of PVA to acid catalyst is 1:0.01-1:0.1, preferably 1:0.03.

[0102] S2.2. Mix butyraldehyde and the type III polyketone crosslinking agent evenly, then slowly add it dropwise to the PVA reaction solution. Heat to the reaction temperature and continue the reaction at this temperature for a period of time. In this step, the type III polyketone crosslinking agent is one or more of trihydroxypropane triacetyl acetate, trihydroxypropane triacetylpropionate, pentaerythritol triacetyl acetate, and pentaerythritol triacetylpropionate. The detailed steps of step S2.2 are as follows:

[0103] Butyraldehyde was added to a type III polyketone crosslinking agent to prepare a mixed solution, which was then added dropwise to the PVA reaction solution under continuous stirring. The temperature was slowly raised to 70°C, and the reaction was carried out for 4 hours to obtain a polyketone crosslinked polyvinyl butyral product, as shown in formula ( As shown in the figure.

[0104]

[0105] The reaction equation is as follows:

[0106]

[0107] Where n is 3, R1 is a straight-chain alkyl group with 1-2 carbon atoms, and R3 is CH3 or OH.

[0108] x, y, z, and m are all integers, with x ranging from 200 to 2500 and y ranging from 20 to 400; the values ​​of z and m are related to the degree of acetalization.

[0109] The degree of polymerization of the raw material PVA is 300-2400, and the degree of alcoholysis is 85-99.9 mol%. Preferably, the degree of polymerization is 500-2000, and the degree of alcoholysis is 95-99 mol%.

[0110] The type III polyketone crosslinking agent is trihydroxypropane triacetyl acetate, trihydroxypropane triacetylpropionate, pentaerythritol triacetyl acetate, and pentaerythritol triacetylpropionate, preferably pentaerythritol triacetylpropionate.

[0111] The reaction time is 4 hours.

[0112] The reaction temperature is between 20-100℃, preferably 70℃.

[0113] The mass ratio of PVA to butyraldehyde is 1:0.1-1:0.5, preferably 1:0.3.

[0114] The mass ratio of PVA to the tri-type polyketide crosslinking agent is 1:0.01-1:0.1, preferably 1:0.05.

[0115] The equipment used is a container equipped with heating and stirring, and various mixers, reaction vessels, and other equipment can be used.

[0116] S2.3. Subsequently, alkali solution is slowly added to adjust the reaction solution to alkalinity to stop the reaction. The product is washed with deionized water, centrifuged, dried to constant weight, and then pulverized to finally obtain polyketide-crosslinked polyvinyl butyral resin. In this step, the pH value at the time of termination is 7-8. The detailed steps of step S2.3 are as follows:

[0117] After the reaction is complete, alkali solution is slowly added to the reaction solution to adjust the pH to 7-8 to stop the reaction. The product is washed with deionized water, centrifuged, dried for several hours to constant weight, and then pulverized to obtain polyketide crosslinked PVB resin powder.

[0118] The alkali may be any one or more combinations of sodium hydroxide, potassium hydroxide, potassium carbonate, or sodium carbonate, preferably sodium hydroxide.

[0119] In the washing process of the product, deionized water is used as the washing solvent.

[0120] The drying process of the product is carried out at a temperature of 40-60℃ and a drying time of 1-6 hours, with the preferred drying temperature being 50℃ and the preferred drying time being 4 hours.

[0121] To further illustrate the technical solution of the present invention, the following embodiments are provided.

[0122] Example 1

[0123] (1) Preparation of ethylene glycol diacetylpropionate

[0124] One eq of ethylene glycol and two eq of levulinic acid were reacted with an acidic catalyst such as tetrabutyl titanate and heated to induce esterification and dehydration, yielding an ester product. This product was then obtained by washing with water, extraction, and vacuum drying to obtain ethylene glycol dilevulinate. This is a conventional esterification reaction, and the preparation method is not unique. This method is presented here for illustrative purposes only, and the corresponding preparation method is not within the scope of this patent.

[0125] (2) Preparation of PVB resin

[0126] 10g of PVA (99% alcoholysis, 2400 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 90g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (10% by mass), then cooled to room temperature. Next, 0.4g of sodium dodecylbenzenesulfonate and 0.3g of concentrated hydrochloric acid were added and stirred to obtain the PVA reaction solution. Separately, 3g of butyraldehyde was added to 1g of ethylene glycol diacetylpropionate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 70℃ over 4 hours until the condensation reaction was complete. Then, sodium hydroxide aqueous solution was slowly added to adjust the pH of the reaction solution to 7 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 4 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder #1 was obtained, with the following structure:

[0127] .

[0128] Example 2

[0129] (1) Preparation of ethylene glycol diacetate

[0130] Two eq of diketene were slowly added dropwise to one eq of ethylene glycol at low temperature, followed by stirring at room temperature for several hours. Finally, ethylene glycol diacetate was obtained by washing with water, extraction, and vacuum drying. This is a conventional ring-opening esterification reaction, and the preparation method is not unique. It is only used for technical illustration purposes, and the corresponding preparation method is not within the scope of protection of this patent.

[0131] (2) Preparation of PVB resin

[0132] 10g of PVA (03-85, degree of hydrolysis 85%, degree of polymerization 300, produced by Sichuan Weihua Chemical Co., Ltd.) and 990g of deionized water were added to a 1.5L beaker. The mixture was stirred and heated at 100℃ until completely dissolved (1% by mass), then cooled to room temperature. Next, 0.2g of sodium cetyl succinate monoester sulfonate and 0.1g of concentrated sulfuric acid were added and stirred to obtain the PVA reaction solution. Separately, 1g of butyraldehyde was added to 0.5g of ethylene glycol diacetate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 20℃ over 4 hours until the condensation reaction was complete. Then, potassium hydroxide aqueous solution was slowly added to adjust the pH of the reaction solution to 7 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 40℃ for 1 hour to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder #2 was obtained, with the following structure:

[0133] .

[0134] Example 3

[0135] (1) Preparation of propylene glycol diacetate

[0136] Replace ethylene glycol with propylene glycol, and the rest of the preparation method is the same as (1) in Example 2.

[0137] (2) Preparation of PVB resin

[0138] Add 10g of PVA (95% alcoholysis, 2000 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 56g of deionized water to a 250mL beaker, stir, and heat at 120℃ until completely dissolved (15% by mass), then cool to room temperature. Next, add 0.6g of sodium fatty alcohol polyoxyethylene ether sulfonate and 1g of concentrated phosphoric acid, stir well to obtain a PVA reaction solution; separately, add 5g of butyraldehyde to 2g of propylene glycol diacetate to prepare a mixed solution, and add it dropwise to the PVA reaction solution over 30 minutes with continuous stirring. Slowly raise the temperature to 100℃ over 4 hours until the condensation reaction is complete; then slowly add potassium carbonate aqueous solution to adjust the reaction solution to pH=8 and maintain this for 30 minutes to stop the reaction. Wash the product 5 times with deionized water, centrifuge, dry at 60℃ for 6 hours to constant weight, and pulverize. Obtain polyketide crosslinked PVB resin powder #3, with the following structure:

[0139] .

[0140] Example 4

[0141] (1) Preparation of propylene glycol diacetylpropionate

[0142] Replace ethylene glycol with propylene glycol, and the rest of the preparation method is the same as (1) in Example 1.

[0143] (2) Preparation of PVB resin

[0144] 10g of PVA (05-99 grade, degree of alcoholysis 99%, degree of polymerization 500, produced by Sichuan Weihua Chemical Co., Ltd.) and 190g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (mass fraction 5%), then cooled to room temperature. Next, 0.3g of sodium dodecylbenzenesulfonate and 0.5g of concentrated hydrochloric acid were added and stirred to obtain the PVA reaction solution. Separately, 2g of butyraldehyde was added to 1.5g of propylene glycol diacetylpropionate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 80℃ over 4 hours until the condensation reaction was complete. Then, sodium carbonate aqueous solution was slowly added to adjust the reaction solution to pH=8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 3 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder #4 was obtained, with the following structure:

[0145] .

[0146] Example 5

[0147] (1) Preparation of butanediol diacetate

[0148] Replace ethylene glycol with butanediol, and the rest of the preparation method is the same as (1) in Example 2.

[0149] (2) Preparation of PVB resin

[0150] 10g of PVA (99% alcoholysis, 1500 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 115g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 95℃ until completely dissolved (8% by mass), then cooled to room temperature. Next, 0.5g of sodium dodecylbenzenesulfonate and 0.2g of concentrated hydrochloric acid were added and stirred to obtain the PVA reaction solution. Separately, 4g of butyraldehyde was mixed with 0.8g of butanediol diacetate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 90℃ over 4 hours until the condensation reaction was complete. Then, sodium hydroxide aqueous solution was slowly added to adjust the reaction solution to pH=8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 55℃ for 2 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder #5 was obtained, with the following structure:

[0151] .

[0152] Example 6

[0153] (1) Preparation of butanediol diacetylpropionate

[0154] Replace ethylene glycol with butanediol, and the rest of the preparation method is the same as (1) in Example 1.

[0155] (2) Preparation of PVB resin

[0156] 10g of PVA (98% alcoholysis, 1700 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 90g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (10% by mass), then cooled to room temperature. Next, 0.4g of sodium dodecylbenzenesulfonate and 0.3g of concentrated hydrochloric acid were added and stirred to obtain the PVA reaction solution. Separately, 3g of butyraldehyde was added to 1g of butanediol diacetylpropionate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 90℃ over 4 hours until the condensation reaction was complete. Then, sodium hydroxide aqueous solution was slowly added to adjust the pH of the reaction solution to 8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 4 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder #6 was obtained, with the following structure:

[0157] .

[0158] Example 7

[0159] (1) Preparation of neopentyl glycol diacetate

[0160] Replace ethylene glycol with neopentyl glycol, and the rest of the preparation method is the same as (1) in Example 2.

[0161] (2) Preparation of PVB resin

[0162] 10g of PVA (98% alcoholysis, 1700 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 90g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (10% by mass), then cooled to room temperature. Next, 0.4g of sodium dodecylbenzenesulfonate and 0.3g of concentrated hydrochloric acid were added and stirred to obtain the PVA reaction solution. Separately, 3g of butyraldehyde was added to 1g of neopentyl glycol diacetate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 90℃ over 4 hours until the condensation reaction was complete. Then, sodium hydroxide aqueous solution was slowly added to adjust the pH of the reaction solution to 8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 4 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder #7 was obtained, with the following structure:

[0163] .

[0164] Example 8

[0165] (1) Preparation of neopentyl glycol diacetylpropionate

[0166] Replace ethylene glycol with neopentyl glycol, and the rest of the preparation method is the same as (1) of Example 1.

[0167] (2) Preparation of PVB resin

[0168] 10g of PVA (98% alcoholysis, 1700 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 90g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (10% by mass), then cooled to room temperature. Next, 0.4g of sodium dodecylbenzenesulfonate and 0.3g of concentrated hydrochloric acid were added and stirred to obtain the PVA reaction solution. Separately, 3g of butyraldehyde was added to 1g of neopentyl glycol diacetylpropionate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 90℃ over 4 hours until the condensation reaction was complete. Then, sodium hydroxide and sodium carbonate aqueous solutions were slowly added to adjust the pH of the reaction solution to 8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 4 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder #8 was obtained, with the following structure:

[0169] .

[0170] Example 9

[0171] (1) Preparation of hexanediol diacetate

[0172] Replace ethylene glycol with hexanediol, and the rest of the preparation method is the same as (1) in Example 2.

[0173] (2) Preparation of PVB resin

[0174] 10g of PVA (17-99 grade, degree of alcoholysis 98%, degree of polymerization 1700, produced by Sichuan Weihua Chemical Co., Ltd.) and 90g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (10% by mass), then cooled to room temperature. Next, 0.4g of sodium dodecylbenzenesulfonate, 0.15g of concentrated hydrochloric acid, and 0.15g of concentrated sulfuric acid were added and stirred to obtain a PVA reaction solution. Separately, 3g of butyraldehyde was added to 1g of hexanediol diacetate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 90℃ over 4 hours until the condensation reaction was complete. Subsequently, sodium hydroxide and potassium hydroxide aqueous solutions were slowly added to adjust the pH of the reaction solution to 8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 4 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder #9 was obtained, with the following structure:

[0175] .

[0176] Example 10

[0177] (1) Preparation of hexanediol diacetylpropionate

[0178] Replace ethylene glycol with hexanediol, and the rest of the preparation method is the same as (1) in Example 1.

[0179] (2) Preparation of PVB resin

[0180] 10g of PVA (98% alcoholysis, 1700 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 90g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (10% by mass), then cooled to room temperature. Next, 0.4g of sodium dodecylbenzenesulfonate, 0.15g of concentrated nitric acid, and 0.15g of concentrated hydrochloric acid were added and stirred to obtain a PVA reaction solution. Separately, 3g of butyraldehyde was added to 1g of hexanediol diacetylpropionate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 90℃ over 4 hours until the condensation reaction was complete. Subsequently, sodium hydroxide and potassium carbonate aqueous solutions were slowly added to adjust the pH of the reaction solution to 8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 4 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder 10# was obtained, with the following structure:

[0181] .

[0182] Example 11

[0183] (1) Preparation of triethylene glycol diacetate

[0184] Replace ethylene glycol with triethylene glycol, and the rest of the preparation method is the same as (1) in Example 2.

[0185] (2) Preparation of PVB resin

[0186] 10g of PVA (98% alcoholysis, 1700 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 90g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (10% by mass), then cooled to room temperature. Next, 0.4g of sodium dodecylbenzenesulfonate and 0.3g of concentrated hydrochloric acid were added and stirred to obtain the PVA reaction solution. Separately, 3g of butyraldehyde was added to 1g of triethylene glycol diacetate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 90℃ over 4 hours until the condensation reaction was complete. Then, sodium hydroxide aqueous solution was slowly added to adjust the pH of the reaction solution to 8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 4 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder 11# was obtained, with the following structure:

[0187] .

[0188] Example 12

[0189] (1) Preparation of triethylene glycol diacetylpropionate

[0190] Replace ethylene glycol with triethylene glycol, and the rest of the preparation method is the same as (1) of Example 1.

[0191] (2) Preparation of PVB resin

[0192] 10g of PVA (98% alcoholysis, 1700 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 90g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (10% by mass), then cooled to room temperature. Next, 0.2g of sodium cetyl succinate monoester sulfonate, 0.2g of sodium dodecylbenzene sulfonate, and 0.3g of concentrated hydrochloric acid were added and stirred to obtain a PVA reaction solution. Separately, 3g of butyraldehyde was added to 1g of triethylene glycol diacetylpropionate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 90℃ over 4 hours until the condensation reaction was complete. Then, sodium hydroxide aqueous solution was slowly added to adjust the pH of the reaction solution to 8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 4 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder 12# was obtained, with the following structure:

[0193] .

[0194] Example 13

[0195] (1) Preparation of diethylene glycol diacetate

[0196] Replace ethylene glycol with diethylene glycol, and the rest of the preparation method is the same as (1) in Example 2.

[0197] (2) Preparation of PVB resin

[0198] 10g of PVA (98% alcoholysis, 1700 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 90g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (10% by mass), then cooled to room temperature. Next, 0.4g of sodium dodecylbenzenesulfonate and 0.3g of concentrated hydrochloric acid were added and stirred to obtain the PVA reaction solution. Separately, 3g of butyraldehyde was added to 1g of diethylene glycol diacetate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 90℃ over 4 hours until the condensation reaction was complete. Then, sodium hydroxide aqueous solution was slowly added to adjust the pH of the reaction solution to 8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 4 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder 13# was obtained, with the following structure:

[0199] .

[0200] Example 14

[0201] (1) Preparation of diethylene glycol diacetylpropionate

[0202] Replace ethylene glycol with diethylene glycol, and the rest of the preparation method is the same as (1) in Example 1.

[0203] (2) Preparation of PVB resin

[0204] 10g of PVA (98% alcoholysis, 1700 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 90g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (10% by mass), then cooled to room temperature. Next, 0.4g of sodium dodecylbenzenesulfonate and 0.3g of concentrated hydrochloric acid were added and stirred to obtain the PVA reaction solution. Separately, 3g of butyraldehyde was added to 1g of diethylene glycol diacetylpropionate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 90℃ over 4 hours until the condensation reaction was complete. Then, sodium hydroxide aqueous solution was slowly added to adjust the pH of the reaction solution to 8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 4 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder 14# was obtained, with the following structure:

[0205] .

[0206] Example 15

[0207] (1) Preparation of pentaerythritol triacetylpropionate

[0208] Replace ethylene glycol with pentaerythritol, change levulinic acid to 3 eq, and the rest of the preparation scheme is the same as (1) of Example 1.

[0209] (2) Preparation of PVB resin

[0210] Add 10g of PVA (99% degree of alcoholysis, 2400 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 90g of deionized water to a 250mL beaker, stir, and heat at 90℃ until completely dissolved (10% by mass), then cool to room temperature. Next, add 0.1g of sodium cetyl succinate monoester sulfonate, 0.1g of sodium fatty alcohol polyoxyethylene ether sulfonate, 0.2g of sodium dodecylbenzene sulfonate, and 0.3g of concentrated hydrochloric acid, and stir well to obtain a PVA reaction solution. Separately, take 3g of butyraldehyde and add 0.5g of pentaerythritol triacetylpropionate to prepare a mixed solution, and add it dropwise to the PVA reaction solution over 30 minutes with continuous stirring. Slowly raise the temperature to 70℃ over 4 hours until the condensation reaction is complete. Then, slowly add sodium hydroxide aqueous solution to adjust the reaction solution to pH=8 and maintain for 30 minutes to stop the reaction. Wash the product 5 times with deionized water, centrifuge, dry at 50℃ for 4 hours to constant weight, and pulverize. Polyketone crosslinked PVB resin powder 15# was obtained, with the following structure:

[0211] .

[0212] Example 16

[0213] (1) Preparation of pentaerythritol triacetylacetate

[0214] Replace ethylene glycol with pentaerythritol, change diketene to 3 eq, and the rest of the preparation scheme is the same as (1) of Example 2.

[0215] (2) Preparation of PVB resin

[0216] 10g of PVA (03-85, degree of alcoholysis 85%, degree of polymerization 300, produced by Sichuan Weihua Chemical Co., Ltd.) and 990g of deionized water were added to a 1.5L beaker. The mixture was stirred and heated at 100℃ until completely dissolved (1% by mass), then cooled to room temperature. Next, 0.2g of sodium cetyl succinate monoester sulfonate and 0.1g of concentrated sulfuric acid were added and stirred to obtain the PVA reaction solution. Separately, 1g of butyraldehyde was added to 0.1g of pentaerythritol triacetyl acetate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 20℃ over 4 hours until the condensation reaction was complete. Then, potassium hydroxide aqueous solution was slowly added to adjust the reaction solution to pH=8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 40℃ for 1 hour to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder 16# was obtained, with the following structure:

[0217] .

[0218] Example 17

[0219] (1) Preparation of trihydroxypropane triacetylacetate

[0220] Replace ethylene glycol with trihydroxypropane, change diketene to 3 eq, and the rest of the preparation scheme is the same as (1) of Example 2.

[0221] (2) Preparation of PVB resin

[0222] Add 10g of PVA (95% alcoholysis, 2000 degree of polymerization, produced by Sichuan Weihua Chemical Co., Ltd.) and 56g of deionized water to a 250mL beaker, stir, and heat at 120℃ until completely dissolved (15% by mass), then cool to room temperature. Next, add 0.6g of sodium fatty alcohol polyoxyethylene ether sulfonate and 1g of concentrated phosphoric acid, stir well to obtain a PVA reaction solution; separately, add 5g of butyraldehyde and 1g of trihydroxypropane triacetate to prepare a mixed solution, and add it dropwise to the PVA reaction solution over 30 minutes with continuous stirring. Slowly raise the temperature to 100℃ over 4 hours until the condensation reaction is complete; then slowly add potassium carbonate aqueous solution to adjust the reaction solution to pH=8 and maintain this for 30 minutes to stop the reaction. Wash the product 5 times with deionized water, centrifuge, dry at 60℃ for 6 hours to constant weight, and pulverize. Obtain polyketide crosslinked PVB resin powder 17#, with the following structure:

[0223] .

[0224] Example 18

[0225] (1) Preparation of trihydroxypropane triacetylpropionate

[0226] Replace ethylene glycol with trihydroxypropane, change levulinic acid to 3 eq, and the rest of the preparation scheme is the same as (1) of Example 1.

[0227] (2) Preparation of PVB resin

[0228] 10g of PVA (05-99, degree of alcoholysis 99%, degree of polymerization 500, produced by Sichuan Weihua Chemical Co., Ltd.) and 190g of deionized water were added to a 250mL beaker. The mixture was stirred and heated at 90℃ until completely dissolved (mass fraction 5%), then cooled to room temperature. Next, 0.3g of sodium dodecylbenzenesulfonate, 0.25g of concentrated nitric acid, and 0.25g of concentrated sulfuric acid were added and stirred to obtain a PVA reaction solution. Separately, 2g of butyraldehyde was added to 0.2g of trihydroxypropane triacetylpropionate to prepare a mixed solution, which was then added dropwise to the PVA reaction solution over 30 minutes with continuous stirring. The temperature was slowly increased to 80℃ over 4 hours until the condensation reaction was complete. Then, sodium carbonate aqueous solution was slowly added to adjust the reaction solution to pH=8 and maintained for 30 minutes to stop the reaction. The product was washed 5 times with deionized water, centrifuged, dried at 50℃ for 3 hours to constant weight, and then pulverized. Polyketone crosslinked PVB resin powder 18# was obtained, with the following structure:

[0229] .

[0230] Comparative Example 1

[0231] Compared with Example 1, the butyraldehyde in Comparative Example 1 was changed to 4g and no type II polyketide crosslinking agent was added, while the remaining steps were the same as in Example 1.

[0232] Comparative Example 2

[0233] Compared with Example 15, the butyraldehyde in Comparative Example 2 was changed to 4g and no tri-type polyketide crosslinking agent was added, while the remaining steps were the same as in Example 15.

[0234] Comparative Example 3

[0235] Choose S-LEC from Sekisui Chemicals, Japan. TM B Series product, model BM-5 (form: powder, viscosity 140-220 MPa.s, acetal degree 68-77%, Tg=73℃).

[0236] Performance testing

[0237] Performance testing of PVB resin when preparing PVB film

[0238] The main relevant properties of the PVB films prepared using the products of Examples 1 and 15, the products of Comparative Examples 1-2, and the commercial product of Comparative Example 3 are shown in Table 1. (There are no special requirements for the preparation of PVB films. Simply choose any commercially available PVB film and replace the raw material PVB resin with the products of Examples 1 and 15, the products of Comparative Examples 1-2, and the commercial product of Comparative Example 3, while keeping other conditions unchanged. An industrially commonly used preparation method is provided here, as shown in Example 1.)

[0239] Example 1

[0240] 1. Preparation of adhesive solution

[0241] In a 500mL beaker equipped with a magnetic stirrer and a thermometer, add 10g of dried PVB resin to constant weight and an appropriate amount of anhydrous ethanol (purity ≥99.7%), and start stirring. A 200W ultrasonic device can be used as an auxiliary device. Stir and sonicate at room temperature for 10-15 minutes until the PVB resin is completely dissolved to prepare a 12% (w / v) transparent adhesive solution.

[0242] 2. Plasticizer addition and degassing

[0243] Weigh 1.5g of triethylene glycol diisooctanoate and add it to the above adhesive solution. Adjust the stirring speed to 350r / min and stir for 30min. Transfer the adhesive solution to a vacuum dryer, adjust the vacuum degree to 0.08MPa, and degas at room temperature for 15min to obtain a bubble-free, uniform, and transparent adhesive solution.

[0244] 3. Template preprocessing

[0245] Take a 20cm×20cm clean glass plate or polytetrafluoroethylene template, wipe the surface repeatedly with anhydrous ethanol to remove oil and impurities; put the clean template into an oven, adjust the temperature to 50℃, preheat at a constant temperature for 10 minutes, and then let it cool naturally to room temperature for later use.

[0246] 4. Precision coating

[0247] (1) Place the pre-treated template stably on a horizontal operating table, install the adjustable coater, and adjust the coating thickness to 0.4 mm for automotive grade as required.

[0248] (2) Slowly pour the degassed adhesive onto one end of the template, start the coating device, and push the coating device along the length of the template at a uniform speed of 2-3 cm / s to ensure that the adhesive evenly covers the template surface without any missed coating or accumulation.

[0249] 5. Gradient drying

[0250] (1) Smoothly move the template coated with adhesive into the fume hood, maintain a ventilation rate of 1-2 m / s, and allow it to evaporate naturally at room temperature for 3-4 hours until a thin hard film forms on the surface of the adhesive and it is no longer sticky.

[0251] (2) Move the template into the drying oven and adjust the temperature to 50±2℃. Dry in stages: keep the temperature at 50℃ for the first 2 hours, raise the temperature to 55℃ for the middle 2 hours, and lower the temperature to 45℃ for the last 1-2 hours. The total drying time is 5-6 hours to ensure that the solvent evaporates completely.

[0252] 6. Unpacking and sorting

[0253] After drying is complete, close the oven and remove the template and film together, allowing them to cool naturally to room temperature. Gently peel the film along the edge with tweezers, avoiding excessive force that could damage the film. Place the peeled PVB film in a clean desiccator and let it stand for 24 hours to eliminate internal stress, thus obtaining a qualified PVB film.

[0254] Table 1 shows the following performance tests performed on PVB film:

[0255] (1) Light transmittance and haze

[0256] Tested according to GB / T 2410-2008.

[0257] (2) Adhesion test

[0258] This test measures the self-adhesive strength of PVB film. Two PVB films were cut to 2.5cm x 15cm dimensions and then completely stacked together. A 0.1mm thick PET film was then layered on each surface of the PVB film laminate. The laminate was then placed between two pieces of glass, and the plates were placed in a press and pressed for 15 minutes at 20-25℃ and 0.25MPa. The PVB laminate was then removed, and a 2cm peel was taken from the end. It was then clamped in the fixture of an electronic universal testing machine, and the peel speed was set to 100mm / min. The 180° peel strength of the two PVB films was measured at 23℃ and 30% humidity.

[0259] The adhesion between PVB film and glass was evaluated, and the results are shown in Table 1 below.

[0260] Table 1 Performance test results of PVB film

[0261] transmittance / % 92.5 91.8 86.1 86.3 89.6 Grayscale / % 0.29 0.32 0.43 0.44 0.38 Adhesion strength N / 25mm 1.78 1.66 1.26 1.24 1.52

[0262] As shown in Table 1, the modified PVB film prepared from polyketone crosslinked polyvinyl butyral resin exhibits superior light transmittance, grayscale, and adhesion compared to PVB films prepared from ordinary PVB. Examples 1 and 2 show significantly better light transmittance and haze than other experimental examples, indicating that the addition of ketone intermediates slows down the reaction rate and prevents excessive local acetalization. Furthermore, the modified PVB contains ester and ether functional groups, resulting in better compatibility with plasticizers and improved optical properties. Combined with Examples 1 and 15 and Comparative Examples 1-3, the addition of crosslinking agents containing two or more ketone functional groups effectively reduces the resin melt index and significantly improves the bonding strength and mechanical properties of PVB. This demonstrates that the PVB film prepared from modified PVB can increase adhesion and optimize light transmittance and haze.

[0263] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0264] 1. In this invention, the polyketone-crosslinked polyvinyl butyral resin prepared as shown in structural formula (I) contains diketone, ester, ether and hydroxyl functional groups, and the polyketone-crosslinked polyvinyl butyral resin prepared as shown in structural formula (II) contains triketone, ester and hydroxyl functional groups. Compared with ordinary polyvinyl butyral resin made only from butyraldehyde, its compatibility with plasticizer, crosslinking uniformity and optical properties of the film are significantly improved.

[0265] 2. In this invention, during the preparation of polyketone-crosslinked polyvinyl butyral resin, the intermediate contains a ketone crosslinking structure that is milder than the aldehyde group, enabling a mild and controllable crosslinking rate and significantly improving the uniformity of resin powder particle size and reaction reproducibility. The crosslinking agent contains two or more ketone functional groups, which can effectively reduce the resin melt index and significantly improve the bonding strength and mechanical properties of PVB. Therefore, the polyketone-crosslinked polyvinyl butyral resin prepared by this invention has high bonding strength, good particle size uniformity, and the preparation method is simple, highly repeatable, and the production process is mild and controllable.

[0266] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A polyketone-crosslinked polyvinyl butyral resin, characterized in that, Having the formula ( The structure shown is as follows: Mode( ); Wherein, R1 is a straight-chain alkyl group with 1-2 carbon atoms, and R2 is an alkyl group with 2-6 carbon atoms or a polyethylene glycol group with a degree of polymerization of 2-3. x, y, z, and m are all integers, with x ranging from 200 to 2500 and y ranging from 20 to 400; the values ​​of z and m are related to the degree of acetalization.

2. A method for preparing the polyketone-crosslinked polyvinyl butyral resin as described in claim 1, characterized in that, Includes the following steps: S1.1 Prepare PVA into an aqueous solution, then add emulsifier and acid catalyst at room temperature and stir until homogeneous to obtain PVA reaction solution; S1.2 Mix butyraldehyde and type II polyketide crosslinking agent evenly, and then slowly add them dropwise to the PVA reaction solution prepared in S1.

1. Heat the mixture to the reaction temperature of 20-100℃ and continue to react at this temperature for 4 hours. S1.

3. Subsequently, sodium hydroxide aqueous solution was slowly added to the product obtained in S1.2 to adjust the reaction solution to alkalinity in order to stop the reaction. The product was washed with deionized water, centrifuged, dried to constant weight, and then pulverized to finally obtain polyketide crosslinked polyvinyl butyral resin.

3. In claim 2, the emulsifier in step S1.1 is one or a mixture of sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate and sodium fatty alcohol polyoxyethylene ether sulfonate (AES), and its amount accounts for 2%-6% of the total PVA; the acid catalyst is one or a mixture of hydrochloric acid, sulfuric acid and phosphoric acid, and its amount accounts for 1%-10% of the total PVA.

4. As claimed in claim 2, the type II polyketide crosslinking agent mentioned in step S1.2 is one of ethylene glycol diacetate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol diacetate, butanediol diacetate, butanediol diacetate, neopentyl glycol diacetate, neopentyl glycol diacetate, hexanediol diacetate, hexanediol diacetate, diethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, and triethylene glycol diacetate, and its amount accounts for 5%-20% of the total PVA.

5. A polyketone-crosslinked polyvinyl butyral resin, characterized in that, Having the formula ( The structure shown is as follows: Mode( ). Where n is 3, R1 is a straight-chain alkyl group with 1-2 carbon atoms, and R3 is CH3 or OH. x, y, z, and m are all integers, with x ranging from 200 to 2500 and y ranging from 20 to 400; the values ​​of z and m are related to the degree of acetalization.

6. A method for preparing the polyketone-crosslinked polyvinyl butyral resin as described in claim 5, characterized in that, Includes the following steps: S2.1 Prepare PVA into an aqueous solution, then add emulsifier and acid catalyst at room temperature and stir until homogeneous to obtain PVA reaction solution; S2.2 Mix butyraldehyde and tri-type polyketide crosslinking agent evenly, and then slowly add it dropwise to the PVA reaction solution prepared in S2.

1. Heat the mixture to the reaction temperature of 20-100℃ and continue to react at this temperature for 4 hours. S2.

3. Subsequently, sodium hydroxide aqueous solution was slowly added to the product obtained in S2.2 to adjust the reaction solution to alkalinity in order to stop the reaction. The product was washed with deionized water, centrifuged, dried to constant weight, and then pulverized to finally obtain polyketide crosslinked polyvinyl butyral resin.

7. In claim 6, the emulsifier in step S2.1 is a mixture of one or more of sodium dodecylbenzene sulfonate (SDBS), sodium cetyl succinate monoester sulfonate and sodium fatty alcohol polyoxyethylene ether sulfonate (AES), and its amount accounts for 2%-6% of the total PVA; the acid catalyst is a mixture of one or more of hydrochloric acid, sulfuric acid and phosphoric acid, and its amount accounts for 1%-10% of the total PVA.

8. As claimed in claim 6, the type III polyketide crosslinking agent mentioned in step S1.2 is one of trihydroxypropane triacetyl acetate, trihydroxypropane triacetylpropionate, pentaerythritol triacetyl acetate, and pentaerythritol triacetylpropionate, and its amount accounts for 1%-10% of the total amount of PVA.

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