CN112375165B - Polyvinyl butyral resin and preparation method thereof - Google Patents
Polyvinyl butyral resin and preparation method thereof Download PDFInfo
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- CN112375165B CN112375165B CN202011218927.4A CN202011218927A CN112375165B CN 112375165 B CN112375165 B CN 112375165B CN 202011218927 A CN202011218927 A CN 202011218927A CN 112375165 B CN112375165 B CN 112375165B
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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Abstract
The invention relates to the technical field of high molecules, in particular to polyvinyl butyral resin and a preparation method thereof. By adding the alkaline organic amine heat stabilizer provided by the invention, the alkaline organic amine heat stabilizer can react with residual acidic substances in resin to inhibit the reaction on PVB resin, so that the prepared PVB resin is not yellowed after being dried in a baking oven at 180 +/-2 ℃ for 4 hours, the quality stability is good, yellowing is avoided in the high-temperature processing process of film making and sheet combining, and other application properties of a product are not influenced; the adopted preparation method ensures thorough reaction, high yield, low energy consumption and low cost, and meets the excellent performances of material oxidation resistance and high transparency; because no emulsifier is added, the washing times of the resin are reduced, water resources are greatly saved, the production cost is reduced, and the environment is protected.
Description
Technical Field
The invention relates to the technical field of high molecules, in particular to polyvinyl butyral resin and a preparation method thereof.
Background
Polyvinyl butyral resin (PVB resin for short) has long branched chains, good flexibility, low glass transition temperature, high tensile strength and impact strength; PVB has excellent transparency, good solubility, good light resistance, water resistance, heat resistance, cold resistance and film forming property, high tensile strength, impact resistance and the like, so the PVB is widely applied to the fields of manufacturing laminated safety glass, adhesives, ceramic stained paper, aluminum foil paper, electrical appliance materials, glass fiber reinforced plastic products, fabric treating agents and the like, and becomes an indispensable resin material.
And the polyvinyl butyral resin is widely applied to the interlayer main material of safety glass because of the excellent cohesiveness and optical performance. The low-end product is used for building safety glass, and the high-end product is used as bulletproof glass of airplanes, tanks and naval vessels in war industry and is also widely used for automobile windshields. The PVB intermediate film is the best adhesive material for manufacturing safety glass in the world at present, and can realize extremely strong adhesive force by being sandwiched between two layers of glass through high-pressure compounding and heating. The safety glass has the characteristics of heat resistance, cold resistance, moisture resistance, impact resistance and high mechanical strength due to the addition of the polyvinyl butyral intermediate film, can realize multiple functions of safety, heat preservation, noise control, ultraviolet isolation and the like, and is widely applied to the building fields of building curtain walls, covering sheds, show windows, bank counters, prison inspection windows, steel furnace screens, various bulletproof glasses and the like, and the industries of automobiles, photovoltaics and the like. Particularly, the PVB intermediate film produced by adopting the special formula can be further applied to the fields of aerospace, military and high and new technology industries and the like, such as airplanes, spacecrafts, military instruments, solar cells, solar receivers and the like.
However, in the current synthesis process of the polyvinyl butyral resin, the main problem is how to control the agglomeration of the polyvinyl butyral resin due to self-adhesion, which affects the post-treatment process, and at present, all major manufacturers control the PVB adhesion by adding an emulsifier, but at the same time, another problem is that the removal of the emulsifier is difficult, a large amount of water is consumed, and the cost is high. If the emulsifier is not completely removed, the adhesive force between the PVB resin film and the glass surface is greatly reduced, the transparency of the laminated safety glass is reduced, and the laminated safety glass is easy to age and turn yellow by heat in the later processing film-making and sheet-combining process. How to adopt a scientific and reasonable preparation process to process and prepare a thermal-stable PVB resin product is a higher requirement of related industries.
In addition, when the PVB film is compounded with glass at high pressure and heated to prepare the safety glass, the PVB film is thermally aged and yellowed due to insufficient thermal stability, so that the use requirement of a user cannot be met. Through analysis, most of plasticizers used for preparing the PVB intermediate film use organic solid acid as a catalyst during synthesis, and a small amount of solid acid still remains after the plasticizer is synthesized and reacts with polyvinyl butyral resin during the preparation of the PVB intermediate film, so that the thermal stability of the PVB film is influenced.
According to the patent technology with the patent number of CN201410083386.7, a certain amount of antioxidant 1076 and emulsifier sodium dodecyl benzene sulfonate are added into raw material butyraldehyde for synthesizing PVB resin, so that the heat resistance stability of the PVB resin can be improved to a certain degree. However, when the PVB resin is used for film making and laminating, certain high temperature is required, the thermal stability of the PVB resin cannot be completely guaranteed to reach the standard, the PVB resin still has the possibility of yellowing in the high-temperature processing process, and the addition of the emulsifier makes the subsequent removal of the emulsifier difficult.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a polyvinyl butyral resin prepared from raw materials including, by weight, 55 to 70 parts of polyvinyl alcohol, 5 to 15 parts of an acid solution, 25 to 35 parts of n-butyraldehyde, and 0.01 to 0.2 part of a heat stabilizer.
As a preferred technical scheme of the invention, the structural formula of the heat stabilizer is shown as follows:
R 1 one or more selected from hydrogen atom, hydroxyalkyl, alkyl, ester group, aryl and derivatives thereof, R 2 One or more selected from hydrogen atom, hydroxyalkyl, alkyl, ester group, aryl and derivatives thereof, R 3 One or more selected from hydrogen atom, hydroxyalkyl, alkyl, ester group, aryl and derivatives thereof.
As a preferred embodiment of the present invention, R 1 One or more selected from hydroxyalkyl, alkyl, aryl and derivatives thereof, R 2 One or more selected from hydroxyalkyl, alkyl, aryl and derivatives thereof, R 3 One or more selected from hydroxyalkyl, alkyl, aryl and derivatives thereof.
In a preferred embodiment of the present invention, the number of carbon atoms in the hydroxyalkyl group is 1 to 4.
In a preferred embodiment of the present invention, the alkyl group is a C1 to C5 alkyl group.
As a preferred technical scheme, the aryl is selected from one or more of phenyl, benzyl, naphthyl, biphenyl, terphenyl and phenanthryl.
In a preferred embodiment of the present invention, the acid in the acid solution is selected from one or more of inorganic acids, organic acids, and inorganic acid salts.
In a preferred embodiment of the present invention, the inorganic acid is selected from one or more of nitric acid, perchloric acid, hydrochloric acid, sulfurous acid, phosphoric acid, and sulfuric acid.
In a second aspect, the present invention provides a method for preparing the polyvinyl butyral resin, which comprises the following steps:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 60-100 ℃, cooling to 15-50 ℃, adding an acid solution and n-butyl aldehyde, and reacting to obtain a crude product mixed solution;
(2) And (3) post-treatment: and neutralizing the mixed solution of the crude product, adding a heat stabilizer, filtering to obtain filter residue, and sequentially washing the filter residue with an alkali solution and water and drying to obtain the polyvinyl butyral resin powder.
As a preferable technical scheme of the present invention, in the step (2), the crude product mixed solution is neutralized by adding an alkali until the pH is 2 to 5, then a heat stabilizer is added, filtration is performed to obtain a filter residue, the filter residue is sequentially washed by an alkali solution until the pH of an effluent liquid is 10 to 14, and then washed by water and dried to obtain the polyvinyl butyral resin powder.
Compared with the prior art, the invention has the following beneficial effects:
1. the heat stabilizer is added, belongs to alkaline organic amine, and can inhibit the reaction with the residual acidic substances in the resin to act on the PVB resin, so that the prepared PVB resin is not yellowed after 4 hours in a baking oven at 180 +/-2 ℃, the quality stability is good, the yellowing cannot occur in the high-temperature processing process of film making and sheet combining, and other application properties of the product are not influenced;
2. the adopted preparation method ensures thorough reaction, high yield, low energy consumption and low cost, and meets the excellent performances of material oxidation resistance and high transparency;
3. because the emulsifier is not added, the washing frequency of the resin is reduced, the water resource is greatly saved, the production cost is reduced, and the environment is protected.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject of the claims rather than immediately after the subject matter, it defines only the elements described in that clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a polyvinyl butyral resin, and the raw materials for preparing the polyvinyl butyral resin comprise, by weight, 55-70 parts of polyvinyl alcohol, 5-15 parts of an acid solution, 25-35 parts of n-butyraldehyde and 0.01-0.2 part of a heat stabilizer.
Polyvinyl alcohol
Polyvinyl alcohol is an organic compound with a chemical formula of [ C2H4O ] n, is white flaky, flocculent or powdery solid in appearance, and is odorless. Is soluble in water (above 95 deg.C), slightly soluble in dimethyl sulfoxide, and insoluble in gasoline, kerosene, vegetable oil, benzene, toluene, dichloroethane, carbon tetrachloride, acetone, ethyl acetate, methanol, and ethylene glycol. Polyvinyl alcohol is an important chemical raw material, and is used for manufacturing polyvinyl acetal, gasoline-resistant pipelines, vinylon synthetic fibers, fabric treating agents, emulsifiers, paper coatings, adhesives, glue and the like. The present invention is not particularly limited to polyvinyl alcohol, and is polyvinyl alcohol known in the art, including, but not limited to, PVA1788, PVA1799, PVA1792, PVA1048, PVA1099, PVA0580, and PVA1588.
Acid solution
In one embodiment, the acid in the acid solution according to the present invention is selected from one or more of inorganic acids, organic acids, and salts of inorganic acids.
Examples of inorganic acids include, but are not limited to, nitric acid, perchloric acid, hydrochloric acid, sulfurous acid, phosphoric acid, sulfuric acid.
Examples of organic acids include, but are not limited to, formic acid, acetic acid, propionic acid, octanoic acid.
Examples of the inorganic acid salt include, but are not limited to, sodium nitrate, sodium perchlorate, sodium chloride, sodium sulfite, disodium hydrogen phosphate, sodium sulfate.
The applicant finds that by adding an acid solution of an inorganic acid as a catalyst, the inorganic acid remained in the polyvinyl butyral filter residue can be removed more easily by acting with a heat stabilizer in the post-treatment process, the washing times are reduced, and the influence on the heat stability is avoided, and preferably, the acid is an inorganic acid; further, the concentration of the acid solution of the present invention is 10 to 40wt%, and 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 37wt%, 40wt% may be mentioned.
The concentration of the acid solution is that the mass of solute in the solution accounts for the weight percentage of the solution, the acid solution is an acid water solution, and the concentration of the acid solution is that the acid accounts for the weight percentage of the acid solution.
Heat stabilizer
In one embodiment, the heat stabilizer of the present invention has the following structural formula:
R 1 one or more selected from hydrogen atom, hydroxyalkyl, alkyl, ester group, aryl and derivatives thereof, R 2 One or more selected from hydrogen atom, hydroxyalkyl, alkyl, ester group, aryl and derivatives thereof, R 3 One or more selected from hydrogen atom, hydroxyalkyl, alkyl, ester group, aryl and derivatives thereof.
The applicant finds that when the N-trisubstituted organic amine heat stabilizer is used, the submission of heat stability is more facilitated compared with a commonly used antioxidant, and the frequency of water washing in post-treatment is reduced, which is probably because the addition of the N-trisubstituted heat stabilizer is more favorable for penetrating into the filter residue of the polyvinyl butyral resin and balancing with the acid action in the filter residue to play a role in emulsifying and dispersing, so that the acid-heat stabilizer is enabled to permeate out of the filter residue in the alkali washing and acid washing processes, the acid residue is avoided, the washing frequency is reduced, and the high temperature resistance and the haze of the finally obtained polyvinyl butyral resin are improved. Preferably, R 1 One or more selected from hydroxyalkyl, alkyl, aryl and derivatives thereof, R 2 One or more selected from hydroxyalkyl, alkyl, aryl and derivatives thereof, R 3 One or more selected from hydroxyalkyl, alkyl, aryl and derivatives thereof.
More preferably, the hydroxyalkyl group of the present invention has 1 to 4 carbon atoms, and examples thereof include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group and a hydroxyisopropyl group.
Further preferably, the alkyl group in the present invention is a C1-C5 alkyl group, and methyl, propyl, isopropyl, or pentyl may be mentioned.
Still more preferably, the aryl group of the present invention is selected from one or more of phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, preferably phenyl, benzyl.
The applicant finds that when a heat stabilizer with hydroxyalkyl, alkyl or aryl groups with a certain carbon chain length as substituents is used, the heat stabilizer can be favorably adsorbed into polymer filter residue in a water system due to a nitrogen-hydrogen bond-free structure on the heat stabilizer when a heat stabilizer with a shorter carbon chain length or an aryl group-containing heat stabilizer with a certain bit group is used, the smaller molecular structure is favorable for the heat stabilizer to penetrate into the filter residue of the polymer in a water system, and acid-base balance is generated between the heat stabilizer and the acid remaining in the filter residue to form a heat stabilizer-acid balance system, so that the heat stabilizer-acid in the filter residue has certain hydrophilicity, the acid in the filter residue can be removed, the high temperature resistance of the polymer is improved through alkali washing and water washing, the haze is reduced, and generally, when the post-treatment water washing is performed, the water washing is generally carried out for more than 10 times by using water which is 2-3 times of the weight of the filter residue, and the applicant finds that when the formula of the polyvinyl butyral resin provided by the invention is adopted, the water washing is only required for 4-5 times, the washing times can be effectively reduced and the water consumption is reduced. And the applicant finds that when the carbon chain on the substituent is too long or the aromatic ring structure is too large, the high lipophilicity and the large bit group prevent the filter residue from permeating, so that trace acid still remains in the filter residue, and the performances of high temperature resistance and the like of the polymer are influenced.
In a second aspect, the present invention provides a method for producing a polyvinyl butyral resin as described above, comprising the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 60-100 ℃, cooling to 15-50 ℃, adding an acid solution and n-butyl aldehyde, and reacting to obtain a crude product mixed solution;
(2) And (3) post-treatment: and neutralizing the mixed solution of the crude product, adding a heat stabilizer, filtering to obtain filter residue, and sequentially washing the filter residue with an alkali solution and water and drying to obtain the polyvinyl butyral resin powder.
In one embodiment, in step (1) of the present invention, polyvinyl alcohol is added into water, mixed at 60-100 ℃, cooled to 15-50 ℃, added with acid solution and n-butyraldehyde, reacted for 10-50 min, and kept for 2-4 h to obtain a crude product mixture.
At present, in order to improve the high temperature resistance and yellowing resistance of the polyvinyl butyral resin, an antioxidant, an emulsifier and the like are added in an acetalization reaction stage, so that more emulsifier, acid and the like are easily wrapped in generated polyvinyl butyral resin precipitate, and the applicant adds the heat stabilizer provided by the invention in a post-treatment stage and performs precipitation with filter residue formed by the polyvinyl butyral resin, so that the preparation is simple, and compared with the addition of the antioxidant, the polyvinyl butyral resin has better high temperature resistance and yellowing resistance, and the haze of a final product is reduced. In one embodiment, in step (2) of the present invention, after neutralizing the crude product mixture to pH 2 to 5, adding a thermal stabilizer, filtering to obtain a filter residue, sequentially washing the filter residue with an alkaline solution until the pH of the effluent is 10 to 14, washing with water, and drying to obtain the polyvinyl butyral resin powder.
In one embodiment, in step (2), the crude product mixture is neutralized to pH 2 to 5, then a heat stabilizer is added, filtration is performed to obtain a filter residue, the filter residue is sequentially washed with an alkaline solution until the pH of the effluent is 10 to 14, and after standing for 0.5 to 2 hours, washed with water and dried at 40 to 70 ℃, so as to obtain the polyvinyl butyral resin powder.
The alkali and alkali solution in step (2) of the present invention is used for adjusting the pH of the solution, and is well known in the art, and examples of the alkali include, but are not limited to, sodium hydroxide and potassium hydroxide.
In one embodiment, in the washing with water of the present invention, the weight ratio of the water to the filter residue is (2 to 3): 1, the number of times of water washing is 4-5.
Examples
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Example 1
The present example provides a polyvinyl butyral resin, which comprises, in parts by weight, 55g of polyvinyl alcohol, 15g of an acid solution, 29.8g of n-butyraldehyde, and 0.2g of a heat stabilizer; the acid solution is a 37wt% hydrochloric acid aqueous solution, and the structural formula of the heat stabilizer is as follows:
the polyvinyl alcohol is purchased from chemical engineering of Changchun (Jiangsu) Co., ltd and is under the brand name BM-17.
This example also provides a method for producing a polyvinyl butyral resin as described above, comprising the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 70 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 15 ℃, adding an acid solution and n-butyl aldehyde, reacting for 40min, and keeping the temperature at 45 ℃ for 3h to obtain a crude product mixed solution;
(2) And (3) post-treatment: and adding the mixed solution of the crude product into an aqueous sodium hydroxide solution to neutralize the mixed solution until the pH value is 4, adding a heat stabilizer, filtering to obtain filter residue, sequentially washing the filter residue with the aqueous sodium hydroxide solution until the pH value of an effluent liquid is 12, standing for 1h, washing with 2 times of water relative to the weight of the filter residue for 5 times, and drying at 50 ℃ to obtain the polyvinyl butyral resin powder.
Example 2
The embodiment provides a polyvinyl butyral resin, and the raw materials for preparing the polyvinyl butyral resin comprise 69.95g of polyvinyl alcohol, 5g of acid solution, 25g of n-butyl aldehyde and 0.05g of heat stabilizer in parts by weight; the acid solution is 37wt% hydrochloric acid aqueous solution, and the structural formula of the heat stabilizer is as follows:
the polyvinyl alcohol is purchased from Changchun chemical industry (Jiangsu) limited company and is under the brand BM-17.
This example also provides a method for producing the polyvinyl butyral resin as described above, including the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 90 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 20 ℃, adding an acid solution and n-butyl aldehyde, reacting for 30min, and keeping the temperature at 50 ℃ for 4h to obtain a crude product mixed solution;
(2) And (3) post-treatment: and adding the mixed solution of the crude product into an aqueous sodium hydroxide solution to neutralize the mixed solution until the pH value is 4, adding a heat stabilizer, filtering to obtain filter residue, sequentially washing the filter residue with the aqueous sodium hydroxide solution until the pH value of an effluent liquid is 12, standing for 1h, washing with 2 times of water relative to the weight of the filter residue for 5 times, and drying at 50 ℃ to obtain the polyvinyl butyral resin powder.
Example 3
This example provides a polyvinyl butyral resin prepared from raw materials comprising, by weight, 59.9g of polyvinyl alcohol, 15g of an acid solution, 25g of n-butyraldehyde and 0.1g of a heat stabilizer; the acid solution is 37wt% hydrochloric acid aqueous solution, and the structural formula of the heat stabilizer is as follows:
the polyvinyl alcohol is purchased from chemical engineering of Changchun (Jiangsu) Co., ltd and is under the brand name BM-17.
This example also provides a method for producing a polyvinyl butyral resin as described above, comprising the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 70 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 15 ℃, adding an acid solution and n-butyl aldehyde, reacting for 40min, and keeping the temperature at 45 ℃ for 3h to obtain a crude product mixed solution;
(2) And (3) post-treatment: and adding the mixed solution of the crude product into an aqueous sodium hydroxide solution to neutralize the mixed solution until the pH value is 4, adding a heat stabilizer, filtering to obtain filter residue, sequentially washing the filter residue with the aqueous sodium hydroxide solution until the pH value of an effluent liquid is 12, standing for 1h, washing with 2 times of water relative to the weight of the filter residue for 5 times, and drying at 50 ℃ to obtain the polyvinyl butyral resin powder.
Example 4
This example provides a polyvinyl butyral resin prepared from raw materials comprising, by weight, 59.99g of polyvinyl alcohol, 10g of an acid solution, 30g of n-butyraldehyde and 0.01g of a heat stabilizer; the acid solution is a 37wt% hydrochloric acid aqueous solution, and the structural formula of the heat stabilizer is as follows:
the polyvinyl alcohol is purchased from chemical engineering of Changchun (Jiangsu) Co., ltd and is under the brand name BM-17.
This example also provides a method for producing a polyvinyl butyral resin as described above, comprising the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 70 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 15 ℃, adding an acid solution and n-butyl aldehyde, reacting for 20min, and keeping the temperature at 45 ℃ for 3.5h to obtain a crude product mixed solution;
(2) And (3) post-treatment: and adding the mixed solution of the crude product into an aqueous sodium hydroxide solution to neutralize the mixed solution until the pH value is 4, adding a heat stabilizer, filtering to obtain filter residue, sequentially washing the filter residue with the aqueous sodium hydroxide solution until the pH value of an effluent liquid is 12, standing for 1h, washing with 2 times of water relative to the weight of the filter residue for 5 times, and drying at 50 ℃ to obtain the polyvinyl butyral resin powder.
Example 5
This example provides a polyvinyl butyral resin, which comprises raw materials, by weight, 64.8g of polyvinyl alcohol, 5g of an acid solution, 30g of n-butyraldehyde, and 0.2g of a heat stabilizer; the acid solution is 37wt% hydrochloric acid aqueous solution, and the structural formula of the heat stabilizer is as follows:
the polyvinyl alcohol is purchased from chemical engineering of Changchun (Jiangsu) Co., ltd and is under the brand name BM-17.
This example also provides a method for producing a polyvinyl butyral resin as described above, comprising the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 85 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 20 ℃, adding an acid solution and n-butyl aldehyde, reacting for 20min, and keeping the temperature at 50 ℃ for 4h to obtain a crude product mixed solution;
(2) And (3) post-treatment: and adding the mixed solution of the crude product into an aqueous sodium hydroxide solution to neutralize the mixed solution until the pH value is 4, adding a heat stabilizer, filtering to obtain filter residue, sequentially washing the filter residue with the aqueous sodium hydroxide solution until the pH value of an effluent liquid is 12, standing for 1h, washing with 2 times of water relative to the weight of the filter residue for 5 times, and drying at 50 ℃ to obtain the polyvinyl butyral resin powder.
Example 6
This example provides a polyvinyl butyral resin prepared from raw materials comprising, by weight, 59.9g of polyvinyl alcohol, 5g of an acid solution, 35g of n-butyraldehyde and 0.1g of a heat stabilizer; the acid solution is 37wt% hydrochloric acid aqueous solution, and the structural formula of the heat stabilizer is as follows:
the polyvinyl alcohol is purchased from chemical engineering of Changchun (Jiangsu) Co., ltd and is under the brand name BM-17.
This example also provides a method for producing a polyvinyl butyral resin as described above, comprising the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 70 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 15 ℃, adding an acid solution and n-butyl aldehyde, reacting for 25min, and keeping the temperature at 45 ℃ for 3h to obtain a crude product mixed solution;
(2) And (3) post-treatment: and adding the mixed solution of the crude product into an aqueous sodium hydroxide solution to neutralize the mixed solution until the pH value is 4, adding a heat stabilizer, filtering to obtain filter residue, sequentially washing the filter residue with the aqueous sodium hydroxide solution until the pH value of an effluent liquid is 12, standing for 1h, washing with 2 times of water relative to the weight of the filter residue for 5 times, and drying at 50 ℃ to obtain the polyvinyl butyral resin powder.
Comparative example 1
The present example provides a polyvinyl butyral resin, which comprises, by weight, 60g of polyvinyl alcohol, 10g of an acid solution, and 30g of n-butyl aldehyde; the acid solution was 37wt% aqueous hydrochloric acid.
The polyvinyl alcohol is purchased from Changchun chemical industry (Jiangsu) limited company and is under the brand BM-17.
This example also provides a method for producing a polyvinyl butyral resin as described above, comprising the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 70 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 15 ℃, adding an acid solution and n-butyl aldehyde, reacting for 20min, and keeping the temperature at 45 ℃ for 3.5h to obtain a crude product mixed solution;
(2) And (3) post-treatment: and adding the mixed solution of the crude product into an aqueous sodium hydroxide solution to neutralize the mixed solution until the pH value is 4, adding a heat stabilizer, filtering to obtain filter residue, sequentially washing the filter residue with the aqueous sodium hydroxide solution until the pH value of an effluent liquid is 12, standing for 1h, washing with 2 times of water relative to the weight of the filter residue for 5 times, and drying at 50 ℃ to obtain the polyvinyl butyral resin powder.
Comparative example 2
This example provides a polyvinyl butyral resin, the raw materials for preparing the polyvinyl butyral resin comprise, by weight, 55g of polyvinyl alcohol, 10g of an acid solution, 34.99g of n-butyraldehyde and 0.01g of a heat stabilizer; the acid solution is 37wt% hydrochloric acid aqueous solution, and the heat stabilizer is antioxidant 1010.
The polyvinyl alcohol is purchased from chemical engineering of Changchun (Jiangsu) Co., ltd and is under the brand name BM-17.
This example also provides a method for producing the polyvinyl butyral resin as described above, including the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 70 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 15 ℃, adding an acid solution and n-butyl aldehyde, reacting for 20min, and keeping the temperature at 45 ℃ for 3.5h to obtain a crude product mixed solution;
(2) And (3) post-treatment: and adding the mixed solution of the crude product into an aqueous sodium hydroxide solution to neutralize the mixed solution until the pH value is 4, adding a heat stabilizer, filtering to obtain filter residue, sequentially washing the filter residue with the aqueous sodium hydroxide solution until the pH value of an effluent liquid is 12, standing for 1h, washing with 2 times of water relative to the weight of the filter residue for 5 times, and drying at 50 ℃ to obtain the polyvinyl butyral resin powder.
Comparative example 3
The present example provides a polyvinyl butyral resin, which comprises, in parts by weight, 59.9g of polyvinyl alcohol, 15g of an acid solution, 25g of n-butyraldehyde, and 0.1g of a heat stabilizer; the acid solution is 37wt% hydrochloric acid aqueous solution, and the heat stabilizer is antioxidant BBT.
The polyvinyl alcohol is purchased from chemical engineering of Changchun (Jiangsu) Co., ltd and is under the brand name BM-17.
This example also provides a method for producing the polyvinyl butyral resin as described above, including the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 70 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 15 ℃, adding an acid solution and n-butyl aldehyde, reacting for 40min, and keeping the temperature at 45 ℃ for 3h to obtain a crude product mixed solution;
(2) And (3) post-treatment: and adding the mixed solution of the crude product into an aqueous sodium hydroxide solution to neutralize the mixed solution until the pH value is 4, adding a heat stabilizer, filtering to obtain filter residue, sequentially washing the filter residue with the aqueous sodium hydroxide solution until the pH value of an effluent liquid is 12, standing for 1h, washing with 2 times of water relative to the weight of the filter residue for 5 times, and drying at 50 ℃ to obtain the polyvinyl butyral resin powder.
Comparative example 4
This example provides a polyvinyl butyral resin, the raw materials for preparing the polyvinyl butyral resin comprise, by weight, 69.8g of polyvinyl alcohol, 5g of an acid solution, 25g of n-butyraldehyde and 0.2g of a heat stabilizer; the acid solution is 37wt% hydrochloric acid aqueous solution, and the heat stabilizer is an antioxidant 1076.
The polyvinyl alcohol is purchased from chemical engineering of Changchun (Jiangsu) Co., ltd and is under the brand name BM-17.
This example also provides a method for producing a polyvinyl butyral resin as described above, comprising the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 90 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 20 ℃, adding an acid solution and n-butyl aldehyde, reacting for 30min, and keeping the temperature at 50 ℃ for 4h to obtain a crude product mixed solution;
(2) And (3) post-treatment: and adding the mixed solution of the crude product into an aqueous sodium hydroxide solution to neutralize the mixed solution until the pH value is 4, adding a heat stabilizer, filtering to obtain filter residue, sequentially washing the filter residue with the aqueous sodium hydroxide solution until the pH value of an effluent liquid is 12, standing for 1h, washing with 2 times of water relative to the weight of the filter residue for 5 times, and drying at 50 ℃ to obtain the polyvinyl butyral resin powder.
Comparative example 5
This example provides a polyvinyl butyral resin prepared from raw materials comprising, by weight, 59.9g of polyvinyl alcohol, 15g of an acid solution, 25g of n-butyraldehyde and 0.1g of a heat stabilizer; the acid solution is 37wt% hydrochloric acid aqueous solution, and the heat stabilizer is diethylamine.
The polyvinyl alcohol is purchased from chemical engineering of Changchun (Jiangsu) Co., ltd and is under the brand name BM-17.
This example also provides a method for producing a polyvinyl butyral resin as described above, comprising the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 70 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 15 ℃, adding an acid solution and n-butyl aldehyde, reacting for 40min, and keeping the temperature at 45 ℃ for 3h to obtain a crude product mixed solution;
(2) And (3) post-treatment: and adding the mixed solution of the crude product into an aqueous sodium hydroxide solution to neutralize the mixed solution until the pH value is 4, adding a heat stabilizer, filtering to obtain filter residue, sequentially washing the filter residue with the aqueous sodium hydroxide solution until the pH value of an effluent liquid is 12, standing for 1h, washing with 2 times of water relative to the weight of the filter residue for 5 times, and drying at 50 ℃ to obtain the polyvinyl butyral resin powder.
Evaluation of Performance
The following experiments were performed as experimental groups provided in the examples.
1. High temperature resistance test: the polyvinyl butyral resin provided in the example was put into an oven at 180 ℃ for 2 hours, 4 hours, and 6 hours, and after being taken out and cooled, the color change was observed to see whether yellowing occurred, and the results are shown in table 1.
TABLE 1 high temperature resistance test
| Whether it is yellowed within 2h | Whether it is yellow or not in 4h | Whether or not it is yellow within 6h | |
| Example 1 | Whether or not | Whether or not | Whether or not |
| Example 2 | Whether or not | Whether or not | Whether or not |
| Example 3 | Whether or not | Whether or not | Is that |
| Example 4 | Whether or not | Whether or not | Whether or not |
| Example 5 | Whether or not | Whether or not | Whether or not |
| Example 6 | Whether or not | Whether or not | Is that |
| Comparative example 1 | Is that | Is that | Is that |
| Comparative example 2 | Is that | Is that | Is that |
| Comparative example 3 | Is that | Is that | Is that |
| Comparative example 4 | Is that | Is that | Is that |
| Comparative example 5 | Whether or not | Is that | Is that |
2. Physical and chemical properties: the polyvinyl formal resins provided in examples 1 to 6 were used in GB/T1723-1993; GB/T2895-2008; GB2410-80; GB/T12010.4-1989; GB-T3682-2000; GB/T16913.3-1997; tests on volatile components, acid values, butyraldehyde groups, viscosity, haze and melt index carried out in GB/T12688.5-1990 all meet the following performance indexes, and the performance indexes are shown in Table 2.
TABLE 2 Performance index
| Test items | Performance index |
| Volatile content% | ≤1.5 |
| Acid value mgKOH/g | ≤0.05 |
| Butyl aldehyde group% | 72.0-78.0 |
| Viscosity(s) | 70-150 |
| Haze degree | ≤0.5 |
| Melt index g/10min | 0.9-1.3 |
3. And (3) impact test: the laminated glass is prepared by taking the polyvinyl formal resin provided by the embodiments 1-6 as an interlayer, and a 630g steel ball is used for impact test (GB 992622005; prEN 12600.
As can be seen from the test results in Table 1, the polyvinyl formal resin prepared by adding the heat stabilizer provided by the invention has significantly increased high temperature resistance, and yellowing is inhibited to a certain extent, and the applicant finds that examples 2 and 4 have good high temperature resistance by adding a small amount of heat stabilizer. And as can be seen from table 2, the polyvinyl butyral resin provided by the invention has high butyraldehyde content and low haze, and when the polyvinyl butyral resin is used for glass interlayer, the prepared laminated safety glass has good strength and impact resistance.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (5)
1. The polyvinyl butyral resin is characterized in that raw materials for preparing the polyvinyl butyral resin comprise, by weight, 55-70 parts of polyvinyl alcohol, 5-15 parts of an acid solution, 25-35 parts of n-butyl aldehyde and 0.01-0.2 part of a heat stabilizer;
the heat stabilizer has a structural formula selected from
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One or more of (a).
2. The polyvinyl butyral resin as claimed in any one of claims 1, wherein the acid in the acid solution is selected from one or more of inorganic acids, organic acids, and salts of inorganic acids.
3. The polyvinyl butyral resin as claimed in claim 2, wherein the inorganic acid is selected from one or more of nitric acid, perchloric acid, hydrochloric acid, sulfurous acid, phosphoric acid, and sulfuric acid.
4. A method for producing the polyvinyl butyral resin as claimed in any one of claims 1 to 3, characterized by comprising the steps of:
(1) Acetalization reaction: adding polyvinyl alcohol into water, mixing at 60-100 ℃, cooling to 15-50 ℃, adding an acid solution and n-butyl aldehyde, and reacting to obtain a crude product mixed solution;
(2) And (3) post-treatment: and neutralizing the mixed solution of the crude product, adding a heat stabilizer, filtering to obtain filter residue, and sequentially washing the filter residue with an alkali solution and water and drying to obtain the polyvinyl butyral resin powder.
5. The method for preparing polyvinyl butyral resin as claimed in claim 4, wherein in the step (2), the crude product mixture is neutralized by adding alkali until the pH value is 2-5, then a heat stabilizer is added, filtration is performed to obtain filter residue, the filter residue is sequentially washed by alkali solution until the pH value of an effluent liquid is 10-14, and then washed by water and dried to obtain polyvinyl butyral resin powder.
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| Title |
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| 山西省化工研究所编.抗氧剂.《塑料橡胶加工助剂（第1版）》.1994,第110-111页. * |
| 王沛等主编.聚乙烯醇缩丁醛的制备.《高分子材料科学实验（第1版）>.2019,第66-68页. * |
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