CN116080032A - PVB intermediate film manufacturing method with regular surface lines - Google Patents
PVB intermediate film manufacturing method with regular surface lines Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08K7/24—Expanded, porous or hollow particles inorganic
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Abstract
The invention discloses a method for manufacturing a PVB intermediate film with regular surface lines, and belongs to the technical field of PVB intermediate film processing. The invention is used for solving the technical problems that the oxidation resistance and mechanical property of a PVB intermediate film in the prior art are to be further improved and the surface pattern retention rate of the PVB intermediate film is low, and the PVB intermediate film manufacturing method with regular surface lines comprises the following steps: PVB resin, N-dimethylformamide and a catalyst are added into a three-neck flask to be stirred and dissolved, dihydro-3- [3- (triethoxysilyl) propyl ] furan-2, 5-dione is added into the three-neck flask, and the temperature of the three-neck flask is increased to 55-65 ℃. The invention not only effectively improves the thermal stability of the PVB intermediate film, so that the PVB film still has higher surface pattern retention rate in a high-temperature state, but also effectively improves the oxidation resistance, tensile strength, elongation at break and knocking value of the PVB intermediate film.
Description
Technical Field
The invention relates to the technical field of PVB intermediate film processing, in particular to a method for manufacturing a PVB intermediate film with regular surface lines.
Background
The PVB intermediate film is a semitransparent film, and is a polymer material formed by plasticizing and extruding polyvinyl butyral resin through a plasticizer. The appearance is a semitransparent film, has no impurities, has a flat surface, certain roughness and good flexibility, is mainly used for laminated glass, has good binding power for inorganic glass, and has the characteristics of transparency, heat resistance, cold resistance, moisture resistance, high mechanical strength and the like.
One chinese patent with publication number CN110655336a in the prior art discloses a PVB film, which is prepared from a PVB composition, wherein the PVB composition comprises, by weight, 60-90 parts of polyvinyl butyral, 1-30 parts of a cross-linking agent system and 1-40 parts of a plasticizer, and the cross-linking agent system comprises, in order of mass ratio, (30-50): (40-60): (5-10) of benzoic acid or a benzoic acid analogue, alkylphenol and anhydride. The oxidation resistance and mechanical property of the PVB film are further improved, when the existing PVB intermediate film is manufactured into laminated glass, a very key process is pre-pressing and exhausting, mainly air between two pieces of glass and one piece of PVB intermediate film is exhausted and is pre-adhered, lines are arranged on the surface of the PVB intermediate film, the pre-pressing and exhausting effect can be effectively improved, the heat stability of the existing PVB intermediate film is poor, the lines on the surface of the PVB intermediate film disappear rapidly after the temperature is increased, the pattern retention rate of the surface of the PVB intermediate film is low, and the pre-pressing and exhausting effect is further improved.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a PVB intermediate film manufacturing method with regular surface grains, which is used for solving the technical problems that the oxidation resistance and mechanical property of a PVB intermediate film in the prior art are required to be further improved, the thermal stability of the existing PVB intermediate film is poor, the surface grains on the PVB intermediate film disappear rapidly after the temperature is increased, and the surface grain retention rate of the PVB intermediate film is low.
The aim of the invention can be achieved by the following technical scheme:
a PVB intermediate film manufacturing method with surface regular grains comprises the following steps:
s1, adding PVB resin, N-dimethylformamide and a catalyst into a three-neck flask, stirring and dissolving, adding dihydro-3- [3- (triethoxysilyl) propyl ] furan-2, 5-dione into the three-neck flask, heating the three-neck flask to 55-65 ℃, reacting for 6-8h, and post-treating to obtain an intermediate I;
the synthesis reaction principle of the intermediate I is as follows:
s2, adding the intermediate I, 3, 5-di-tert-butyl-4-hydroxybenzoic acid, N-dimethylformamide and a catalyst into a three-neck flask, stirring, increasing the temperature of the three-neck flask to 140-150 ℃, reacting for 4-6h, and post-treating to obtain modified PVB resin;
the synthesis reaction principle of the modified PVB resin is as follows:
s3, adding the modified PVB resin, the modified silicon resin, tetrahydrofuran and activated carbon into a flask, stirring, heating the three-neck flask to 60-65 ℃, reacting for 1.5-3h, and post-treating to obtain the composite resin;
s4, uniformly mixing the composite resin and the plasticizer, and then adding the mixture into an extruder for extrusion to obtain a sheet PVB composite film with the thickness of 0.38-1.52 mm;
s5, embossing the PVB composite film, and forming regular lines on the surface of the PVB composite film to prepare the PVB intermediate film.
Further, in the step S1, the weight ratio of PVB resin, dihydro-3- [3- (triethoxysilyl) propyl ] furan-2, 5-dione, N-dimethylformamide and catalyst is 5:2:12:0.05, and the catalyst is zinc chloride or calcium chloride.
Further, the weight ratio of the intermediate I to the 3, 5-di-tert-butyl-4-hydroxybenzoic acid to the N, N-dimethylformamide to the catalyst is 5:0.5:12:0.015, and the catalyst is any one of tetraethyl titanate, tetraisopropyl titanate, tetrapropyl titanate, tetrabutyl titanate, isopropyl zirconate and N-propyl zirconate.
Further, the preparation of the modified silicone resin comprises the following steps:
a1, adding tetraethoxysilane, diphenyl dimethoxy silane, methylphenyl dimethoxy silane, dimethyl diethoxy silane, hydrochloric acid, dimethylbenzene and butanol into a three-neck flask, stirring, raising the temperature of the three-neck flask to 70-80 ℃, reacting for 2-3h, dropwise adding n-butylamine into the three-neck flask, regulating the pH value of the system to be 7, and separating liquid;
a2, transferring the organic phase into a three-neck flask with a water separator, stirring, raising the temperature of the three-neck flask to 115-125 ℃, reacting for 2-3h, lowering the temperature of the three-neck flask to 85-90 ℃, and distilling under reduced pressure until no liquid flows out to obtain the modified silicone resin.
The synthetic reaction principle of the modified resin is as follows:
further, in the step A1, the weight ratio of the tetraethoxysilane, the diphenyldimethoxysilane, the methylphenyldimethoxysilane, the dimethyldiethoxysilane, the hydrochloric acid, the xylene and the butanol is 12:5:2:5:15:40:8, wherein the concentration of the hydrochloric acid is 5mol/L.
Further, the weight ratio of the modified PVB resin to the modified silicone resin to the tetrahydrofuran to the activated carbon in the step S3 is 3:2:8:1.5, and the post-treatment operation in the step S3 comprises the following steps: and after the reaction is finished, carrying out suction filtration, transferring filtrate into a rotary evaporator, setting the temperature to be 45-55 ℃, and carrying out reduced pressure distillation until no liquid flows out, thereby obtaining the composite resin.
Further, in the step S4, the weight ratio of the composite resin to the plasticizer is 1:0.08, and the plasticizer is composed of one or more of dioctyl phthalate, diglyceride phthalate and diisodecyl phthalate.
Further, six sections of temperatures of the extruder feed cylinder from the feed end to the discharge end are 150 ℃, 220 ℃, 225 ℃, 230 ℃ and 230 ℃ respectively, the rotating speed of a main machine screw is 35r/min, and the PVB composite film is obtained after being extruded from a die head, subjected to water cooling rapid prototyping and then dried by a dehumidifier and a dryer in sequence.
Further, the embossing process includes the steps of:
b1, treating a PVB composite film supercooling water tank, and setting the temperature of the supercooling water tank to be-5-5 ℃;
b2, dewatering the PVB composite film treated by the supercooling water tank sequentially through an air knife and two groups of water absorbing rollers to obtain a low-temperature PVB composite;
and B3, introducing the low-temperature PVB compound to a press roll unit, and setting the compression stress of the press roll and the low-temperature PVB compound film to be 20-60KN to obtain the PVB intermediate film.
The invention has the following beneficial effects:
1. when the PVB intermediate film with regular surface grains is prepared, through the reaction of the tetraethoxysilane, the diphenyl dimethoxy silane, the methyl phenyl dimethoxy silane and the dimethyl diethoxy silane in an acidic environment, the siloxane on the tetraethoxysilane, the diphenyl dimethoxy silane, the methyl phenyl dimethoxy silane and the dimethyl diethoxy silane is hydrolyzed to generate the silicon hydroxyl, and under the high temperature effect, the silicon hydroxyl is dehydrated and condensed to form the modified silicon resin with a reticular structure, so that the tensile strength and the elongation at break of the PVB intermediate film are effectively improved, the embedding of phenyl siloxane chain segments is realized, the oxidation stability of the modified silicon resin is endowed, the thermal stability of the modified silicon resin is effectively improved, and the patterns formed on the surface after the low-temperature embossing treatment still have good surface pattern retention rate in the high temperature environment.
2. In the preparation of the PVB intermediate film with regular surface lines, after PVB resin is dissolved by N, N-dimethylformamide, under the condition of a catalyst, the carboxyl on the modified PVB resin is prepared by grafting 3, 5-di-tert-butyl-4-hydroxybenzoic acid to the PVB resin, the polarity of the PVB resin is effectively improved, the compatibility of the modified PVB resin and the modified silicone resin is promoted, the modified PVB resin can be fully mixed together with the modified silicone resin, after the active carbon is used for mixing the modified PVB resin with the modified silicone resin, the decoloration degree of the composite resin is improved, the modified silicone resin is grafted to the PVB resin, the 3, 5-di-tert-butyl-4-hydroxybenzoic acid is subjected to esterification reaction under the condition of the catalyst, the carboxyl on the modified PVB resin is prepared, the compatibility of the modified PVB resin and the modified silicone resin is promoted, the modified PVB resin is fully mixed together, the modified PVC resin is decolored, the modified PVC resin is well mixed with the modified silicone resin, the modified silicone resin is simultaneously, the modified PVC resin is well mixed with the modified with the 3, the modified silicone resin is stretched, the modified glass is fully mixed with the modified silicone resin, the modified glass is stretched, the modified glass is well, the modified glass has the tensile strength of the modified PVC resin is further improved, and the modified glass is well, and the tensile strength of the modified glass is improved, and the modified glass is better, and the tensile strength is improved, effectively improves the oxidation resistance of the composite resin.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The method for manufacturing the PVB intermediate film with the regular surface lines provided by the embodiment comprises the following steps:
s1, preparing modified PVB resin
Weighing the following components in parts by weight: adding 100g of PVB resin, 240g of N, N-dimethylformamide and 1.0g of zinc chloride into a three-neck flask, stirring and dissolving, adding 40g of dihydro-3- [3- (triethoxysilyl) propyl ] furan-2, 5-dione into the three-neck flask, heating the three-neck flask to 55 ℃, reacting for 6 hours, reducing the temperature of the three-neck flask to room temperature, adding 480g of acetone into the three-neck flask, stirring for 30 minutes to obtain a dispersion liquid, taking the other flask, adding 2.2kg of purified water into the flask, stirring, slowly adding the dispersion liquid into the flask, precipitating solids, filtering, transferring a filter cake into an oven with the temperature of 60 ℃, and drying for 8 hours to obtain an intermediate I;
weighing the following components in parts by weight: 100g of intermediate I, 10g of 3, 5-di-tert-butyl-4-hydroxybenzoic acid, 240g of N, N-dimethylformamide and 0.3g of tetraethyl titanate are added
Stirring in a three-neck flask, raising the temperature of the three-neck flask to 140 ℃, reacting for 4 hours, completing the reaction, reducing the temperature of the three-neck flask to room temperature, adding 480g of acetone into the three-neck flask, stirring for 30 minutes to obtain a dispersion liquid, taking the other flask, adding 2.2kg of purified water into the flask, stirring, slowly adding the dispersion liquid into the flask, precipitating solids, filtering, transferring a filter cake into an oven with the temperature of 70 ℃ and drying for 8 hours to obtain the modified PVB resin.
S2, preparing modified silicone resin
Weighing the following components in parts by weight: 60g of tetraethoxysilane, 25g of diphenyl dimethoxy silane, 10g of methylphenyl dimethoxy silane, 25g of dimethyl diethoxy silane, 75g of 5mol/L hydrochloric acid, 200g of dimethylbenzene and 40g of butanol are added into a three-neck flask, stirred, the temperature of the three-neck flask is increased to 70 ℃, the reaction is carried out for 2 hours, n-butylamine is added into the three-neck flask in a dropwise manner to adjust the pH=7, the mixture is kept stand for 15 minutes, and the liquid is separated;
transferring the organic phase into a three-neck flask with a water separator, stirring, raising the temperature of the three-neck flask to 115 ℃, reacting for 2 hours, timely removing water in the water separator in the reaction process, reducing the temperature of the three-neck flask to 85 ℃ after the reaction is completed, constructing the three-neck flask into a distillation device, and performing reduced pressure distillation until no liquid flows out, thereby obtaining the modified silicone resin.
S3, preparing cast composite resin
Weighing the following components in parts by weight: 90g of modified PVB resin, 60g of modified silicon resin, 240g of tetrahydrofuran and 12g of activated carbon are added into a flask for stirring, the temperature of the three-neck flask is increased to 60 ℃, the reaction is completed for 1.5h, the suction filtration is carried out, the filtrate is transferred into a rotary evaporator, the temperature is set to 45 ℃, and the reduced pressure distillation is carried out until no liquid flows out, thus obtaining the composite resin.
S4, preparing PVB composite film
Weighing the following components in parts by weight: 500g of composite resin and 40g of diisodecyl phthalate are uniformly mixed and then added into an extruder for extrusion, six sections of temperatures from a feeding end to a discharging end of an extruder charging barrel are respectively 150 ℃, 220 ℃, 225 ℃, 230 ℃ and 230 ℃, the rotating speed of a host screw is 35r/min, PVB composite film is extruded from a die head and is rapidly molded through water cooling, and then is dried through a dehumidifier and a dryer in sequence to obtain the sheet PVB composite film with the thickness of 1.32mm, wherein the temperature of the dryer is 85 ℃, and the drying time is 20s.
S5, preparing PVB intermediate film
Treating a PVB composite film supercooling water tank, wherein a 20wt% sodium chloride aqueous solution is contained in the cooling water tank, and the temperature of the cooling water tank is set to be minus 5 ℃;
sequentially removing water from the PVB composite film treated by the supercooling water tank through an air knife and two groups of water absorbing rollers to obtain a low-temperature PVB composite with the temperature of-5 ℃ and no water drops on the surface;
the low-temperature PVB compound is introduced to a compression roller unit consisting of two metal embossing rollers, a hydraulic device, a pressure sensor and an integral metal frame, the two ends of each embossing roller can be subjected to gap adjustment through hydraulic screw transmission, the pressure stress between each embossing roller and a PVB compound film is monitored to be 20+/-2 KN through the pressure sensor arranged on the unit, and regular grains are formed on the surface of the PVB compound film, so that a PVB intermediate film is obtained.
Example 2
The method for manufacturing the PVB intermediate film with the regular surface lines provided by the embodiment comprises the following steps:
s1, preparing modified PVB resin
Weighing the following components in parts by weight: adding 100g of PVB resin, 240g of N, N-dimethylformamide and 1.0g of calcium chloride into a three-neck flask, stirring and dissolving, adding 40g of dihydro-3- [3- (triethoxysilyl) propyl ] furan-2, 5-dione into the three-neck flask, heating the three-neck flask to 60 ℃, reacting for 7 hours, reducing the temperature of the three-neck flask to room temperature, adding 480g of acetone into the three-neck flask, stirring for 35 minutes to obtain a dispersion liquid, taking the other flask, adding 2.2kg of purified water into the flask, stirring, slowly adding the dispersion liquid into the flask, precipitating solids, filtering, transferring a filter cake into an oven with the temperature of 68 ℃, and drying for 9 hours to obtain an intermediate I;
weighing the following components in parts by weight: 100g of intermediate I, 10g of 3, 5-di-tert-butyl-4-hydroxybenzoic acid, 240g of N, N-dimethylformamide and 0.3g of tetraisopropyl titanate are added into a three-neck flask to be stirred, the temperature of the three-neck flask is increased to 140 ℃, the reaction is completed for 4 hours, the temperature of the three-neck flask is reduced to room temperature, 480g of acetone is added into the three-neck flask, stirring is carried out for 30 minutes, a dispersion liquid is obtained, another flask is taken, 2.2kg of purified water is added into the flask to be stirred, the dispersion liquid is slowly added into the flask, solids are separated out, filtering is carried out, and a filter cake is transferred into an oven with the temperature of 75 ℃ to be dried for 9 hours, thus obtaining the modified PVB resin.
S2, preparing modified silicone resin
Weighing the following components in parts by weight: 60g of tetraethoxysilane, 25g of diphenyl dimethoxy silane, 10g of methylphenyl dimethoxy silane, 25g of dimethyl diethoxy silane, 75g of 5mol/L hydrochloric acid, 200g of dimethylbenzene and 40g of butanol are added into a three-neck flask, stirred, the temperature of the three-neck flask is increased to 75 ℃, the reaction is carried out for 2.5 hours, n-butylamine is added dropwise into the three-neck flask to adjust the pH=7 of the system, the mixture is kept stand for 20 minutes, and the liquid is separated;
transferring the organic phase into a three-neck flask with a water separator, stirring, raising the temperature of the three-neck flask to 120 ℃, reacting for 2.5h, timely removing water in the water separator in the reaction process, reducing the temperature of the three-neck flask to 87 ℃ after the reaction is completed, constructing the three-neck flask into a distillation device, and distilling under reduced pressure until no liquid flows out, thereby obtaining the modified silicone resin.
S3, preparing cast composite resin
Weighing the following components in parts by weight: 90g of modified PVB resin, 60g of modified silicon resin, 240g of tetrahydrofuran and 12g of activated carbon are added into a flask for stirring, the temperature of the three-neck flask is increased to 63 ℃, the reaction is completed for 2.5h, the suction filtration is carried out, the filtrate is transferred into a rotary evaporator, the temperature is set to 50 ℃, and the reduced pressure distillation is carried out until no liquid flows out, thus obtaining the composite resin.
S4, preparing PVB composite film
Weighing the following components in parts by weight: the method comprises the steps of mixing 500g of composite resin and 40g of phthalic acid diester uniformly, adding the mixture into an extruder for extrusion, setting six sections of temperatures from a feeding end to a discharging end of an extruder charging barrel to be 150 ℃, 220 ℃, 225 ℃, 230 ℃ and 230 ℃ respectively, and enabling a host screw to rotate at 35r/min, extruding the PVB composite film from a die head, performing water cooling rapid prototyping, and sequentially drying the PVB composite film through a dehumidifier and a dryer to obtain a sheet PVB composite film with the thickness of 1.28mm, wherein the temperature of the dryer is 88 ℃, and the drying time is 25s.
S5, preparing PVB intermediate film
Treating a PVB composite film supercooling water tank, wherein a 20wt% sodium chloride aqueous solution is contained in the cooling water tank, and the temperature of the cooling water tank is set to be 0 ℃;
sequentially removing water from the PVB composite film treated by the supercooling water tank through an air knife and two groups of water absorbing rollers to obtain a low-temperature PVB composite with the surface having 0-5 ℃ and no water drops;
the low-temperature PVB compound is introduced to a compression roller unit consisting of two metal embossing rollers, a hydraulic device, a pressure sensor and an integral metal frame, the two ends of each embossing roller can be subjected to gap adjustment through hydraulic screw transmission, the pressure stress between each embossing roller and a PVB compound film is monitored to be 40+/-2 KN through the pressure sensor arranged on the unit, and regular grains are formed on the surface of the PVB compound film, so that a PVB intermediate film is obtained.
Example 3
The method for manufacturing the PVB intermediate film with the regular surface lines provided by the embodiment comprises the following steps:
s1, preparing modified PVB resin
Weighing the following components in parts by weight: adding 100g of PVB resin, 240g of N, N-dimethylformamide and 1.0g of zinc chloride into a three-neck flask, stirring and dissolving, adding 40g of dihydro-3- [3- (triethoxysilyl) propyl ] furan-2, 5-dione into the three-neck flask, heating the three-neck flask to 65 ℃, reacting for 8 hours, reducing the temperature of the three-neck flask to room temperature, adding 480g of acetone into the three-neck flask, stirring for 40 minutes to obtain a dispersion liquid, taking the other flask, adding 2.2kg of purified water into the flask, stirring, slowly adding the dispersion liquid into the flask, precipitating solids, filtering, transferring a filter cake into an oven with the temperature of 75 ℃, and drying for 10 hours to obtain an intermediate I;
weighing the following components in parts by weight: 100g of intermediate I, 10g of 3, 5-di-tert-butyl-4-hydroxybenzoic acid, 240g of N, N-dimethylformamide and 0.3g of tetrabutyl titanate are added into a three-neck flask to be stirred, the temperature of the three-neck flask is increased to 150 ℃, the reaction is completed, the temperature of the three-neck flask is reduced to room temperature, 480g of acetone is added into the three-neck flask, stirring is carried out for 40min, a dispersion liquid is obtained, another flask is taken, 2.2kg of purified water is added into the flask to be stirred, the dispersion liquid is slowly added into the flask, solid is separated out, filtering is carried out, and a filter cake is transferred into an oven with the temperature of 80 ℃ to be dried for 10h, thus obtaining the modified PVB resin.
S2, preparing modified silicone resin
Weighing the following components in parts by weight: 60g of tetraethoxysilane, 25g of diphenyl dimethoxy silane, 10g of methylphenyl dimethoxy silane, 25g of dimethyl diethoxy silane, 75g of 5mol/L hydrochloric acid, 200g of dimethylbenzene and 40g of butanol are added into a three-neck flask, stirred, the temperature of the three-neck flask is increased to 80 ℃, the reaction is carried out for 3 hours, n-butylamine is added into the three-neck flask in a dropwise manner to adjust the pH=7, and the mixture is kept stand for 25 minutes, and is separated;
transferring the organic phase into a three-neck flask with a water separator, stirring, raising the temperature of the three-neck flask to 125 ℃, reacting for 3 hours, timely removing water in the water separator in the reaction process, reducing the temperature of the three-neck flask to 90 ℃ after the reaction is completed, constructing the three-neck flask into a distillation device, and performing reduced pressure distillation until no liquid flows out, thereby obtaining the modified silicone resin.
S3, preparing cast composite resin
Weighing the following components in parts by weight: 90g of modified PVB resin, 60g of modified silicon resin, 240g of tetrahydrofuran and 12g of activated carbon are added into a flask for stirring, the temperature of the three-neck flask is increased to 65 ℃, the reaction is completed for 3 hours, the suction filtration is carried out, the filtrate is transferred into a rotary evaporator, the temperature is set to 55 ℃, and the reduced pressure distillation is carried out until no liquid flows out, thus obtaining the composite resin.
S4, preparing PVB composite film
Weighing the following components in parts by weight: 500g of composite resin and 40g of dioctyl phthalate are uniformly mixed and then added into an extruder for extrusion, six sections of temperatures from a feeding end to a discharging end of an extruder charging barrel are respectively 150 ℃, 220 ℃, 225 ℃, 230 ℃ and 230 ℃, the rotating speed of a host screw is 35r/min, PVB composite film is extruded from a die head and is rapidly molded through water cooling, and then is dried through a dehumidifier and a dryer in sequence to obtain the sheet PVB composite film with the thickness of 1.30mm, wherein the temperature of the dryer is 90 ℃, and the drying time is 30s.
S5, preparing PVB intermediate film
Treating a PVB composite film supercooling water tank, wherein a 20wt% sodium chloride aqueous solution is contained in the cooling water tank, and the temperature of the cooling water tank is set to be 5 ℃;
sequentially removing water from the PVB composite film treated by the supercooling water tank through an air knife and two groups of water absorbing rollers to obtain a low-temperature PVB composite with the surface having 0-5 ℃ and no water drops;
the low-temperature PVB compound is introduced to a compression roller unit consisting of two metal embossing rollers, a hydraulic device, a pressure sensor and an integral metal frame, the two ends of each embossing roller can be subjected to gap adjustment through hydraulic screw transmission, the pressure stress between each embossing roller and a PVB compound film is controlled to be 60+/-2 KN through the pressure sensor arranged on the unit, and regular grains are formed on the surface of the PVB compound film, so that a PVB intermediate film is obtained.
Comparative example 1
This comparative example differs from example 3 in that the dihydro-3- [3- (triethoxysilyl) propyl ] furan-2, 5-dione in step S1 is replaced by an equivalent amount of phthalic anhydride.
Comparative example 2
The present comparative example differs from example 3 in that diphenyldimethoxysilane and methylphenyldimethoxysilane were not added in step S2.
Comparative example 3
This comparative example differs from example 3 in that the modified PVB resin in step S3 was replaced by an equivalent amount of intermediate I.
Performance test:
the PVB intermediate film prepared in examples 1 to 3 and comparative examples 1 to 3 was tested for tensile strength, elongation at break, strike value, 180 DEG peel strength, ultraviolet aging resistance and surface pattern retention, wherein the PVB intermediate film was tested for tensile strength, elongation at break, strike value, 180 DEG peel strength and ultraviolet aging resistance with reference to the standard JG/T449-2014 polyvinyl butyral (PVB) adhesive film for building photovoltaic module, and the surface pattern retention was tested by cutting the PVB intermediate film into a 10X 10cm sample, placing the sample in an oven at 80℃for 15 minutes, taking out the sample, calculating the area of the portion of the PVB intermediate film where the pattern disappeared, and then, according to the formula: the surface pattern retention was calculated by 1-pattern decimal place area/sample area x 100%, the amount of change in yellow index was measured as yellow index before and after aging according to the above criteria, and then the following formula was followed: (after aging yellow index-before aging yellow index)/before aging yellow index x 100% and the specific test results are shown in the following table:
from the analysis of the performance test data in the above table, it is known that:
by combining the data of examples 1-3 and comparative examples 1-3, the invention prepares the modified silicone resin with phenyl siloxane chain segments by hydrolyzing and condensing tetraethoxysilane, diphenyl dimethoxy silane, methyl phenyl dimethoxy silane and dimethyl diethoxy silane, effectively improves the thermal stability of the silicone resin, and improves the compatibility and oxidation resistance of the modified PVB resin and the modified silicone resin after modifying PVB resin by dihydro-3- [3- (triethoxy silicon) propyl ] furan-2, 5-dione and 3, 5-di-tert-butyl-4-hydroxybenzoic acid, thereby improving the tensile strength, elongation at break, oxidation resistance and surface pattern retention rate of the composite resin.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (9)
1. The PVB intermediate film manufacturing method with the regular surface lines is characterized by comprising the following steps of:
s1, adding PVB resin, N-dimethylformamide and a catalyst into a three-neck flask, stirring and dissolving, adding dihydro-3- [3- (triethoxysilyl) propyl ] furan-2, 5-dione into the three-neck flask, heating the three-neck flask to 55-65 ℃, reacting for 6-8h, and post-treating to obtain an intermediate I;
s2, adding the intermediate I, 3, 5-di-tert-butyl-4-hydroxybenzoic acid, N-dimethylformamide and a catalyst into a three-neck flask, stirring, increasing the temperature of the three-neck flask to 140-150 ℃, reacting for 4-6h, and post-treating to obtain modified PVB resin;
s3, adding the modified PVB resin, the modified silicon resin, tetrahydrofuran and activated carbon into a flask, stirring, heating the three-neck flask to 60-65 ℃, reacting for 1.5-3h, and post-treating to obtain the composite resin;
s4, uniformly mixing the composite resin and the plasticizer, and then adding the mixture into an extruder for extrusion to obtain a sheet PVB composite film with the thickness of 0.38-1.52 mm;
s5, embossing the PVB composite film, and forming regular lines on the surface of the PVB composite film to prepare the PVB intermediate film.
2. The method for producing a PVB interlayer film having regular surface lines according to claim 1, wherein in the step S1, the weight ratio of the PVB resin, the dihydro-3- [3- (triethoxysilyl) propyl ] furan-2, 5-dione, the N, N-dimethylformamide, and the catalyst is 5:2:12:0.05, and the catalyst is zinc chloride or calcium chloride.
3. The method for manufacturing the PVB intermediate film with the regular surface lines according to claim 1, wherein the weight ratio of the intermediate I to the 3, 5-di-tert-butyl-4-hydroxybenzoic acid to the N, N-dimethylformamide to the catalyst is 5:0.5:12:0.015, and the catalyst is any one of tetraethyl titanate, tetraisopropyl titanate, tetrapropyl titanate, tetrabutyl titanate, isopropyl zirconate and N-propyl zirconate.
4. The method for manufacturing the PVB intermediate film with the regular surface lines as set forth in claim 1, wherein the preparation of the modified silicone resin comprises the following steps:
a1, adding tetraethoxysilane, diphenyl dimethoxy silane, methylphenyl dimethoxy silane, dimethyl diethoxy silane, hydrochloric acid, dimethylbenzene and butanol into a three-neck flask, stirring, raising the temperature of the three-neck flask to 70-80 ℃, reacting for 2-3h, dropwise adding n-butylamine into the three-neck flask, regulating the pH value of the system to be 7, and separating liquid;
a2, transferring the organic phase into a three-neck flask with a water separator, stirring, raising the temperature of the three-neck flask to 115-125 ℃, reacting for 2-3h, lowering the temperature of the three-neck flask to 85-90 ℃, and distilling under reduced pressure until no liquid flows out to obtain the modified silicone resin.
5. The method for producing a PVB interlayer film having regular surface lines according to claim 4, wherein in the step A1, the weight ratio of ethyl orthosilicate, diphenyldimethoxysilane, methylphenyldimethoxysilane, dimethyldiethoxysilane, hydrochloric acid, xylene, and butanol is 12:5:2:5:15:40:8, wherein the concentration of the hydrochloric acid is 5mol/L.
6. The method for manufacturing the PVB intermediate film with the regular surface lines according to claim 1, wherein the weight ratio of the modified PVB resin to the modified silicone resin to the tetrahydrofuran to the activated carbon in the step S3 is 3:2:8:1.5, and the post-treatment operation in the step S3 comprises: and after the reaction is finished, carrying out suction filtration, transferring filtrate into a rotary evaporator, setting the temperature to be 45-55 ℃, and carrying out reduced pressure distillation until no liquid flows out, thereby obtaining the composite resin.
7. The method for producing a PVB interlayer film having regular surface lines according to claim 1, wherein in the step S4, the weight ratio of the composite resin to the plasticizer is 1:0.08, and the plasticizer is one or more of dioctyl phthalate, di-phthalate, and diisodecyl phthalate.
8. The method for manufacturing the PVB intermediate film with the regular surface lines according to claim 1, wherein six sections of temperatures from a feeding end to a discharging end of the extruder charging barrel are 150 ℃, 220 ℃, 225 ℃, 230 ℃ and 230 ℃ respectively, the rotating speed of a host screw is 35r/min, and the PVB composite film is obtained after being extruded from a die head, rapidly molded through water cooling, and then dried through a dehumidifier and a dryer in sequence.
9. A method of making a PVB interlayer film having regular surface texture as described in claim 1 wherein said embossing comprises the steps of:
b1, treating a PVB composite film supercooling water tank, and setting the temperature of the supercooling water tank to be-5-5 ℃;
b2, dewatering the PVB composite film treated by the supercooling water tank sequentially through an air knife and two groups of water absorbing rollers to obtain a low-temperature PVB composite;
and B3, introducing the low-temperature PVB compound to a press roll unit, and setting the compression stress of the press roll and the low-temperature PVB compound film to be 20-60KN to obtain the PVB intermediate film.
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