CN117417469A - Efficient polyvinyl butyral resin and preparation method thereof - Google Patents
Efficient polyvinyl butyral resin and preparation method thereof Download PDFInfo
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- CN117417469A CN117417469A CN202311557458.2A CN202311557458A CN117417469A CN 117417469 A CN117417469 A CN 117417469A CN 202311557458 A CN202311557458 A CN 202311557458A CN 117417469 A CN117417469 A CN 117417469A
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- butyral resin
- polyvinyl butyral
- polyvinyl alcohol
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 title claims abstract description 78
- 229920005989 resin Polymers 0.000 title claims abstract description 65
- 239000011347 resin Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 68
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 67
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000005406 washing Methods 0.000 claims abstract description 27
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- -1 alkyl diamine Chemical class 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 9
- 239000003995 emulsifying agent Substances 0.000 abstract description 18
- 230000001804 emulsifying effect Effects 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000005336 safety glass Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000005340 laminated glass Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- YJGHMLJGPSVSLF-UHFFFAOYSA-N 2-[2-(2-octanoyloxyethoxy)ethoxy]ethyl octanoate Chemical compound CCCCCCCC(=O)OCCOCCOCCOC(=O)CCCCCCC YJGHMLJGPSVSLF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of resins, in particular to a high-efficiency polyvinyl butyral resin and a preparation method thereof. The high-efficiency polyvinyl butyral resin comprises polyvinyl alcohol, n-butyraldehyde, acid, modified polyvinyl alcohol, dipentaerythritol and water. The invention also provides a preparation method of the composite. Compared with the prior art, the invention provides the high-efficiency polyvinyl butyral resin, no emulsifier is needed to be added in the production process, the polyvinyl butyral resin is prepared by taking polyvinyl alcohol and n-butyraldehyde as raw materials and taking modified polyvinyl alcohol and dipentaerythritol as additives through catalytic reaction, the modified polyvinyl alcohol is adopted to replace the emulsifier added in the traditional polyvinyl butyral production, and the high-efficiency polyvinyl butyral resin has good dispersing and emulsifying properties, and the process of removing the emulsifier by washing with a large amount of water in the production process is avoided. The preparation method provided by the invention omits a large amount of water washing process, saves a large amount of water resources, reduces the production cost and protects the environment.
Description
Technical Field
The invention relates to the technical field of resins, in particular to a high-efficiency polyvinyl butyral resin and a preparation method thereof.
Background
Polyvinyl butyral (PVB) resin is a white solid particle with good optical properties and is widely used in the fields of aviation, automobiles, construction, photovoltaics, paint, textile, glass interlayers, etc.;
with the rapid development of the fields of construction industry, automobile industry, photovoltaic industry and the like, the demand for high-performance and high-efficiency polyvinyl butyral resin is gradually increased; however, the PVB resin needs to be continuously treated at a higher temperature (150-200 ℃) in the process of processing and manufacturing the safety glass intermediate film, and in the process, the phenomena of yellowing, hardening and the like are easy to occur due to aging and degradation of the PVB resin, self-polymerization and oxidation of residual butyraldehyde and the like.
The polyvinyl butyral is polymerized by polyvinyl alcohol and butyraldehyde under acid catalysis, the crosslinking degree is difficult to control in the polymerization process, the quality of resin is not guaranteed, and at present, all domestic large-scale manufacturers control the polyvinyl butyral resin by adding an emulsifying agent, but the emulsifying agent needs to consume a large amount of water in the subsequent treatment process, and has high cost and complex process.
CN105001357a discloses a continuous preparation method for synthesizing polyvinyl butyral resin by organic acid catalysis, which is characterized in that: preparation of 500 parts by mass of a polyvinyl alcohol-n-butyraldehyde aqueous emulsion, and continuous feeding of 100 parts by mass of a 2.5% aqueous organic acid solution into a high shear mixer at 50S -1 -150S -1 The mixture is mixed and reacted for 10min to 20min under the shearing rate of 50Pa to 150Pa and the shearing force of 30 ℃ to 40 ℃, then the mixture is sent to an aging kettle, and the polymerization process is completed by the reaction of a first section of 3 to 4h at 39 ℃ to 41 ℃ and a second section of 2 to 3h at 59 ℃ to 61 ℃; removing mother liquor by a centrifugal machine, washing a solid by water, alkali washing, washing by water and drying to obtain powdery polyvinyl butyral resin; the invention has the advantages of continuous preparation, high efficiency, low energy consumption and stable product quality; the prepared polyvinyl butyral resin is suitable for the fields of photovoltaic packaging materials, building safety glass, automobile safety glass and the like. However, the process is complicated, a large amount of water is needed for washing, a large amount of water resources are wasted, and the performance is still further improved.
Disclosure of Invention
In order to achieve the above object, the present invention provides a highly effective polyvinyl butyral resin, characterized in that: comprises polyvinyl alcohol, n-butyraldehyde, acid, modified polyvinyl alcohol, dipentaerythritol and water.
Further preferably, the high-efficiency polyvinyl butyral resin comprises the following raw materials in parts by weight:
50-100 parts by weight of polyvinyl alcohol
10-50 parts by weight of n-butyraldehyde
Acid 5-10 weight portions
1-6 parts by weight of modified polyvinyl alcohol
Dipentaerythritol 5-8 weight portions
300-600 parts by weight of water
The acid is one or a mixture of more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid and perchloric acid;
the concentration of the acid is 10-40wt%;
the preparation method of the modified polyvinyl alcohol comprises the following steps:
adding 2-3 parts by weight of polyvinyl alcohol into 50-80 parts by weight of water, soaking for 30-60min, adding 1-10 parts by weight of 5-10wt% sodium hydroxide solution, heating to 60-80 ℃ for reacting for 40-80min, adding 1-2 parts by weight of modifier, keeping the temperature of 60-80 ℃ for reacting for 2-3h, carrying out reduced pressure distillation for treatment after the reaction is finished, and drying to obtain the modified polyvinyl alcohol.
The preparation method of the modifier comprises the following steps:
adding 3-6 parts by weight of alkyl diamine into 80-120 parts by weight of methanol, and uniformly mixing to obtain an alkyl diamine solution; adding 25-33 parts by weight of 2, 3-epoxypropyl trimethyl ammonium chloride into 40-60 parts by weight of methanol, and uniformly mixing to obtain a 2, 3-epoxypropyl trimethyl ammonium chloride solution; adding 2, 3-epoxypropyl trimethyl ammonium chloride solution into alkyl diamine solution, heating to 80-90 ℃ for reaction for 4-6h, and after the reaction is finished, distilling under reduced pressure to remove methanol, crystallizing, filtering and drying to obtain the modifier.
The alkyl diamine is at least one of nonylenediamine and decylenediamine.
The present invention is not particularly limited to polyvinyl alcohol and is well known in the art including, but not limited to, PVA1788, PVA1799, PVA1792, PVA1048, PVA1099, PVA0580, PVA1588.
The invention takes the alkyl diamine and the 2, 3-epoxypropyl trimethyl ammonium chloride as raw materials to prepare the modifier, and the modifier is used for modifying the polyvinyl alcohol, so that the invention has good emulsifying and dispersing properties; the polyvinyl alcohol has low cost, the water solubility in the later modification stage is enhanced, the dosage is small, the satisfactory emulsifying effect can be achieved, meanwhile, the modified polyvinyl alcohol is adopted to replace the emulsifying agent added in the traditional polyvinyl butyral production, the polyvinyl alcohol has good dispersing and emulsifying properties, and the process of removing the emulsifying agent by washing with a large amount of water in the production process is avoided.
The invention provides a high-efficiency polyvinyl butyral resin, which does not need to add an emulsifier in the production process, takes polyvinyl alcohol and n-butyraldehyde as raw materials, takes modified polyvinyl alcohol and dipentaerythritol as additives, prepares the polyvinyl butyral resin through catalytic reaction, adopts modified polyvinyl alcohol to replace the emulsifier added in the traditional polyvinyl butyral production, has good dispersion and emulsifying properties, avoids a process of washing with a large amount of water to remove the emulsifier in the production process, and greatly improves the branching degree of the polyvinyl butyral by introducing dipentaerythritol and improves the weather resistance of products.
The preparation method provided by the invention omits a large amount of water washing process, saves a large amount of water resources, reduces the production cost and protects the environment.
The application also discloses a preparation method of the high-efficiency polyvinyl butyral resin.
A preparation method of high-efficiency polyvinyl butyral resin comprises the following steps:
step 1, adding polyvinyl alcohol into water, uniformly mixing, and then adding modified polyvinyl alcohol, uniformly mixing to obtain a mixed solution;
step 2, adding 1/3-1/2 of n-butyraldehyde into the mixed solution, uniformly mixing, heating to 80-90 ℃, adding 1/3-1/2 of acid, keeping the temperature of 80-90 ℃ for continuous reaction for 2-4h, and cooling to 25-35 ℃;
and step 3, continuously adding dipentaerythritol and residual n-butyraldehyde, heating to 65-80 ℃, adding residual acid, continuously reacting for 1-2 hours, cooling to room temperature after the reaction is finished, filtering to obtain precipitate, washing with water, soaking for 30-60 minutes by adopting 5-10wt% sodium hydroxide aqueous solution, washing with water, and drying to obtain the high-efficiency polyvinyl butyral resin.
The step condensation reaction is adopted in the application, and meanwhile, the dipentaerythritol is added so that the polyvinyl butyral has good weather resistance.
The invention has the beneficial effects that:
the invention provides a high-efficiency polyvinyl butyral resin, which does not need to add an emulsifier in the production process, takes polyvinyl alcohol and n-butyraldehyde as raw materials, takes modified polyvinyl alcohol and dipentaerythritol as additives, prepares the polyvinyl butyral resin through catalytic reaction, adopts modified polyvinyl alcohol to replace the emulsifier added in the traditional production of the polyvinyl butyral, has good dispersion and emulsification properties, and avoids a process of removing the emulsifier by washing with a large amount of water in the production process. The preparation method provided by the invention omits a large amount of water washing process, saves a large amount of water resources, reduces the production cost and protects the environment.
Detailed Description
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present invention.
Introduction of raw materials used in the examples of the present invention:
the polyvinyl alcohol used in the examples was PVA1788.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent 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 high-efficiency polyvinyl butyral resin consists of the following raw materials in parts by weight:
polyvinyl alcohol 100 parts by weight
40 parts by weight of n-butyraldehyde
6 parts by weight of 20% by weight hydrochloric acid
600 parts by weight of water
The preparation method of the efficient polyvinyl butyral resin comprises the following steps:
step 1, adding polyvinyl alcohol into water, and uniformly mixing to obtain a polyvinyl alcohol aqueous solution;
step 2, adding 1/2 n-butyraldehyde into the polyvinyl alcohol aqueous solution, heating to 85 ℃, adding 1/2 hydrochloric acid, keeping the temperature of 85 ℃ for continuous reaction for 3 hours, and cooling to 25 ℃;
and step 3, continuously adding the rest n-butyraldehyde, heating to 80 ℃, adding the rest hydrochloric acid, continuously reacting for 1h, cooling to room temperature after the reaction is finished, filtering, taking precipitate, washing with water, soaking for 60min by using a 5wt% sodium hydroxide aqueous solution, washing with water, and drying to obtain the high-efficiency polyvinyl butyral resin.
Example 2
The high-efficiency polyvinyl butyral resin consists of the following raw materials in parts by weight:
polyvinyl alcohol 100 parts by weight
40 parts by weight of n-butyraldehyde
6 parts by weight of 20% by weight hydrochloric acid
Modified polyvinyl alcohol 5 weight portions
Dipentaerythritol 5 weight portions
600 parts by weight of water
The preparation method of the modified polyvinyl alcohol comprises the following steps:
s1, adding 5 parts by weight of decamethylene diamine into 100 parts by weight of methanol, and uniformly mixing to obtain a decamethylene diamine solution; adding 32.1 parts by weight of 2, 3-epoxypropyl trimethyl ammonium chloride into 50 parts by weight of methanol, and uniformly mixing to obtain a 2, 3-epoxypropyl trimethyl ammonium chloride solution; adding 2, 3-epoxypropyl trimethyl ammonium chloride solution into decanediamine solution, heating to 90 ℃ for reaction for 6 hours, and after the reaction is finished, distilling under reduced pressure to remove methanol, crystallizing, filtering and drying to obtain a modifier;
s2, adding 3.2 parts by weight of polyvinyl alcohol into 50 parts by weight of water, soaking for 60min, adding 8 parts by weight of 5wt% sodium hydroxide aqueous solution, heating to 80 ℃ for reaction for 80min, adding 1.5 parts by weight of the modifier in the step S1, keeping the temperature for reaction for 3h, and performing reduced pressure distillation for treatment and drying after the reaction is finished to obtain the modified polyvinyl alcohol.
A preparation method of high-efficiency polyvinyl butyral resin comprises the following steps:
step 1, adding polyvinyl alcohol into water, uniformly mixing, and then adding modified polyvinyl alcohol, uniformly mixing to obtain a mixed solution;
step 2, adding 1/2 formula amount of n-butyraldehyde into the mixed solution, uniformly mixing, heating to 85 ℃, adding 1/2 formula amount of hydrochloric acid, keeping the temperature of 85 ℃ for continuous reaction for 3 hours, and cooling to 25 ℃;
and step 3, continuously adding dipentaerythritol and residual n-butyraldehyde, heating to 80 ℃, adding residual hydrochloric acid, continuously reacting for 1h, cooling to room temperature after the reaction is finished, filtering to obtain precipitate, washing with water, soaking for 60min by adopting a 5wt% sodium hydroxide aqueous solution, washing with water, and drying to obtain the high-efficiency polyvinyl butyral resin.
Example 3
The high-efficiency polyvinyl butyral resin consists of the following raw materials in parts by weight:
polyvinyl alcohol 100 parts by weight
40 parts by weight of n-butyraldehyde
6 parts by weight of 20% by weight hydrochloric acid
Dipentaerythritol 5 weight portions
600 parts by weight of water
A preparation method of high-efficiency polyvinyl butyral resin comprises the following steps:
step 1, adding polyvinyl alcohol into water, and uniformly mixing to obtain a polyvinyl alcohol aqueous solution;
step 2, adding 1/2 formula amount of n-butyraldehyde into the polyvinyl alcohol aqueous solution, heating to 85 ℃, adding 1/2 formula amount of hydrochloric acid, keeping the temperature of 85 ℃ for continuous reaction for 3 hours, and cooling to 25 ℃;
and step 3, continuously adding dipentaerythritol and residual n-butyraldehyde, heating to 80 ℃, adding residual hydrochloric acid, continuously reacting for 1h, cooling to room temperature after the reaction is finished, filtering to obtain precipitate, washing with water, soaking for 60min by adopting a 5wt% sodium hydroxide aqueous solution, washing with water, and drying to obtain the high-efficiency polyvinyl butyral resin.
Example 4
The high-efficiency polyvinyl butyral resin consists of the following raw materials in parts by weight:
polyvinyl alcohol 100 parts by weight
50 parts by weight of n-butyraldehyde
10 parts by weight of 20% by weight hydrochloric acid
6 parts by weight of modified polyvinyl alcohol
Dipentaerythritol 8 weight portions
600 parts by weight of water
The preparation method of the modified polyvinyl alcohol is identical to that of the example 2.
A preparation method of high-efficiency polyvinyl butyral resin comprises the following steps:
step 1, adding polyvinyl alcohol into water, uniformly mixing, and then adding modified polyvinyl alcohol, uniformly mixing to obtain a mixed solution;
step 2, adding 1/2 formula amount of n-butyraldehyde into the mixed solution, uniformly mixing, heating to 85 ℃, adding 1/2 formula amount of hydrochloric acid, keeping the temperature of 85 ℃ for continuous reaction for 3 hours, and cooling to 25 ℃;
and step 3, continuously adding dipentaerythritol and residual n-butyraldehyde, heating to 80 ℃, adding residual hydrochloric acid, continuously reacting for 1h, cooling to room temperature after the reaction is finished, filtering to obtain precipitate, washing with water, soaking for 60min by adopting a 5wt% sodium hydroxide aqueous solution, washing with water, and drying to obtain the high-efficiency polyvinyl butyral resin.
Example 5
The high-efficiency polyvinyl butyral resin consists of the following raw materials in parts by weight:
polyvinyl alcohol 100 parts by weight
10 parts by weight of n-butyraldehyde
5 parts by weight of 20% by weight hydrochloric acid
1 part by weight of modified polyvinyl alcohol
Dipentaerythritol 5 weight portions
600 parts by weight of water
The preparation method of the modified polyvinyl alcohol is identical to that of the example 2.
A preparation method of high-efficiency polyvinyl butyral resin comprises the following steps:
step 1, adding polyvinyl alcohol into water, uniformly mixing, and then adding modified polyvinyl alcohol, uniformly mixing to obtain a mixed solution;
step 2, adding 1/2 formula amount of n-butyraldehyde into the mixed solution, uniformly mixing, heating to 85 ℃, adding 1/2 formula amount of hydrochloric acid, keeping the temperature of 85 ℃ for continuous reaction for 3 hours, and cooling to 25 ℃;
and step 3, continuously adding dipentaerythritol and residual n-butyraldehyde, heating to 80 ℃, adding residual hydrochloric acid, continuously reacting for 1h, cooling to room temperature after the reaction is finished, filtering to obtain precipitate, washing with water, soaking for 60min by adopting a 5wt% sodium hydroxide aqueous solution, washing with water, and drying to obtain the high-efficiency polyvinyl butyral resin.
Test example 1
The acid value test was carried out on the high-efficiency polyvinyl butyral resin prepared in the examples with reference to GB/T2895-2008 determination of partial acid value and total acid value of Plastic polyester resin;
reference is made to GB/T12688.5-2019 section 5 of Industrial styrene test method: the butyraldehyde group test is carried out on the high-efficiency polyvinyl butyral resin prepared in the example by a titration method for determining the total aldehyde content;
the viscosity test was carried out on the high-efficiency polyvinyl butyral resin prepared in the examples with reference to GB/T1723-1993 coating viscosity measurement;
the haze test is carried out on the high-efficiency polyvinyl butyral resin prepared in the example by referring to GB2410-2008 determination of light transmittance and haze of transparent plastics;
determination of melt Mass Flow Rate (MFR) and melt volume flow Rate (MVR) of plastics thermoplastics, section 1, see GB/T3682.1-2018: the melt index test was performed on the high efficiency polyvinyl butyral resin prepared in the examples;
TABLE 1 test results of high Performance polyvinyl butyral resin
As shown in Table 1, the acid value of the high-efficiency polyvinyl butyral resin prepared by the invention is less than or equal to 0.05mgKOH/g, the butyraldehyde group content is less than or equal to 71-77%, the viscosity is 98-130S, the haze is less than or equal to 0.4, and the melt index is 0.9-1.3g/10min.
Test example 2
80 parts by weight of the high-efficiency polyvinyl butyral resin prepared in each example and 0.05 part by weight of antioxidant 1010 are respectively added into a stirrer, stirred for 20min at a rotating speed of 1000rpm, and the material temperature is controlled at 50 ℃; finally 21 parts by weight of triethylene glycol di-octanoate are added at 20rpm and stirred for 10 minutes. Then put into a double-screw extruder, the temperature of the screw is set at 150 ℃, the temperature of the die is set at 165 ℃, and the PVB film with uniform thickness is prepared through plasticizing, tape casting, cooling, molding and rolling in sequence.
Tensile strength and elongation at break were tested with reference to GB/T32020-2015;
TABLE 2 results of mechanical properties of polyvinyl butyral resin films
Test example 3
Cutting the PVB film prepared in the test example 2 into pieces of 400mm multiplied by 400mm, respectively clamping the pieces of glass with clean surfaces between the pieces of glass, placing the pieces of glass into a silica gel bag for sealing, pumping air for 15min under the vacuum degree of 2.5KPa, heating the pieces of glass to 90 ℃ for pumping air for 15min, then placing the pieces of glass into an autoclave, hot-pressing the pieces of glass for 30 min under the pressure of 1.3MPa and the temperature of 135 ℃, and preserving heat for 2h to prepare the PVB laminated glass.
Light transmittance test is carried out by referring to GB/T2680-2021 determination of visible light transmittance, solar direct transmittance, solar total transmittance, ultraviolet transmittance and related window glass parameters of building glass;
table 3 light transmittance test results
| Transmittance/% | |
| Example 1 | 76.39 |
| Example 2 | 91.24 |
| Example 3 | 83.67 |
| Example 4 | 88.40 |
| Example 5 | 86.15 |
From tables 2 to 3, it is clear that the PVB film and PVB laminated glass prepared from the high-efficiency polyvinyl butyral resin obtained in example 2 have good mechanical properties and light transmittance, respectively; the invention takes the alkyl diamine and the 2, 3-epoxypropyl trimethyl ammonium chloride as raw materials to prepare the modifier, and the modifier is used for modifying the polyvinyl alcohol, so that the invention has good emulsifying and dispersing properties; the polyvinyl alcohol has low cost, the water solubility in the later modification stage is enhanced, the dosage is small, the satisfactory emulsifying effect can be achieved, meanwhile, the modified polyvinyl alcohol is adopted to replace the emulsifying agent added in the traditional polyvinyl butyral production, the polyvinyl alcohol has good dispersing and emulsifying properties, and the process of removing the emulsifying agent by washing with a large amount of water in the production process is avoided.
The invention provides a high-efficiency polyvinyl butyral resin, which does not need to add an emulsifier in the production process, takes polyvinyl alcohol and n-butyraldehyde as raw materials, takes modified polyvinyl alcohol and dipentaerythritol as additives, prepares the polyvinyl butyral resin through catalytic reaction, adopts modified polyvinyl alcohol to replace the emulsifier added in the traditional polyvinyl butyral production, has good dispersion and emulsifying properties, avoids a process of washing with a large amount of water to remove the emulsifier in the production process, and greatly improves the branching degree of the polyvinyl butyral by introducing dipentaerythritol and improves the weather resistance of products.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (9)
1. A high-efficiency polyvinyl butyral resin is characterized in that: including polyvinyl alcohol, n-butyraldehyde, acid, water.
2. The high efficiency polyvinyl butyral resin of claim 1, wherein: also included are modified polyvinyl alcohols.
3. The high efficiency polyvinyl butyral resin of claim 1, wherein: dipentaerythritol is also included.
4. The high efficiency polyvinyl butyral resin of claim 3, wherein: the material consists of the following raw materials in parts by weight:
50-100 parts by weight of polyvinyl alcohol
10-50 parts by weight of n-butyraldehyde
Acid 5-10 weight portions
1-6 parts by weight of modified polyvinyl alcohol
Dipentaerythritol 5-8 weight portions
300-600 parts by weight of water.
5. The high efficiency polyvinyl butyral resin according to claim 1 or 4, wherein: the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid and perchloric acid.
6. The high efficiency polyvinyl butyral resin according to claim 5, wherein: the concentration of the acid is 10-40wt%.
7. The high efficiency polyvinyl butyral resin according to claim 2 or 4, wherein: the preparation method of the modified polyvinyl alcohol comprises the following steps:
and (3) adding polyvinyl alcohol into water for soaking, then adding sodium hydroxide solution, heating for reaction, then adding a modifier, keeping the reaction, carrying out reduced pressure distillation for treatment after the reaction is finished, and drying to obtain the modified polyvinyl alcohol.
8. The high efficiency polyvinyl butyral resin of claim 7, wherein: the preparation method of the modifier comprises the following steps:
adding alkyl diamine into methanol, and uniformly mixing to obtain an alkyl diamine solution; adding 2, 3-epoxypropyl trimethyl ammonium chloride into methanol, and uniformly mixing to obtain a 2, 3-epoxypropyl trimethyl ammonium chloride solution; adding 2, 3-epoxypropyl trimethyl ammonium chloride solution into alkyl diamine solution, heating for reaction, distilling under reduced pressure to remove methanol after the reaction is finished, crystallizing, filtering and drying to obtain the modifier.
9. A process for preparing the high efficiency polyvinyl butyral resin according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
step 1, adding polyvinyl alcohol into water, uniformly mixing, and then adding modified polyvinyl alcohol, uniformly mixing to obtain a mixed solution;
step 2, adding 1/3-1/2 of n-butyraldehyde into the mixed solution, uniformly mixing, heating to 80-90 ℃, adding 1/3-1/2 of acid, keeping the temperature of 80-90 ℃ for continuous reaction for 2-4h, and cooling to 25-35 ℃;
and step 3, continuously adding dipentaerythritol and residual n-butyraldehyde, heating to 65-80 ℃, adding residual acid, continuously reacting for 1-2 hours, cooling to room temperature after the reaction is finished, filtering to obtain precipitate, washing with water, soaking for 30-60 minutes by adopting 5-10wt% sodium hydroxide aqueous solution, washing with water, and drying to obtain the high-efficiency polyvinyl butyral resin.
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