CN113512903A - Modified polyvinyl alcohol and corrugated case moisture absorption strength retention agent containing same - Google Patents
Modified polyvinyl alcohol and corrugated case moisture absorption strength retention agent containing same Download PDFInfo
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- CN113512903A CN113512903A CN202110472299.0A CN202110472299A CN113512903A CN 113512903 A CN113512903 A CN 113512903A CN 202110472299 A CN202110472299 A CN 202110472299A CN 113512903 A CN113512903 A CN 113512903A
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- polyvinyl alcohol
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
- B31B—MAKING CONTAINERS OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
- B31B50/00—Making rigid or semi-rigid containers, e.g. boxes or cartons
- B31B50/74—Auxiliary operations
- B31B50/742—Coating; Impregnating; Waterproofing; Decoating
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/26—Aminoplasts
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Abstract
The invention discloses modified polyvinyl alcohol and a corrugated case moisture absorption strength retention agent containing the same; the method comprises the following steps: adding modified polyvinyl alcohol, urea, paraformaldehyde, low-carbon alcohol and sodium hydroxide into a dispersion medium, and uniformly stirring and mixing to obtain a mixed material; and heating the mixed material to 85-100 ℃, adding an aldehyde capturing agent, continuing stirring for 1-3 h, cooling to room temperature, adding a pH regulator to regulate the pH value, and thus obtaining the moisture absorption strength maintaining agent for the corrugated case. The modified polyvinyl alcohol is prepared by modifying polyvinyl alcohol with benzoyl oxidized paeoniflorin. The modified polyvinyl alcohol with certain hydrophobic property is used as a component of a moisture absorption strength retaining agent of the corrugated case in the corrugated case, so that the corrugated case has high ring crush strength and folding endurance, and has excellent moisture resistance and stiffness, and the corrugated case with excellent quality is obtained.
Description
Technical Field
The invention belongs to the technical field of papermaking additives, and particularly relates to modified polyvinyl alcohol and a corrugated case moisture absorption strength retention agent containing the same.
Background
Corrugated paper boxes are ideal packaging containers, have the characteristics of lightness, firmness, vibration reduction and suitability for mechanized production, and are used for transport packaging and sale packaging for many years. However, the corrugated board used at present has some problems: for example, the corrugated cardboard has poor mechanical properties such as strength and the like, is easy to damage or tear, is not very good in moisture-proof effect, limits the application of the corrugated cardboard in a humid environment, and cannot meet the requirements of high-performance packaging corrugated cardboard boxes. The mode of solving at present has the dampproofing protective layer of one deck again of cover in the outside of carton, but has increased the packing cost, and still another mode is at the carton outside coating one deck dampproof agent, and this kind of mode need solve the adhesion of dampproof agent and carton and the problem that the dampproof agent easily peeled off, at present, all does not reach the effect of ideal.
Gonlun Yun (science and technology information of small and medium-sized enterprises, 1994(03):11) discloses a moisture-proof technology for plastic-coated corrugated cases, and the moisture-proof paint is coated on the corrugated cases by adopting a glue rolling and stamping paint method; the moisture-proof coating comprises the following components: 1 kg of polyvinyl butyral, 1-14 kg of 95% ethanol, 40-50 g of dioctyl phthalate and 150 g of glycerol modified rosin; the dissolving of polyvinyl butyral is carried out by providing an enamel reaction tank with stirring device, and providing it with corresponding condenser and auxiliary tools.
Disclosure of Invention
The invention aims to provide modified polyvinyl alcohol with certain hydrophobic property, which is used as a component of a moisture absorption strength retaining agent of a corrugated case in the corrugated case, so that the corrugated case has higher ring crush strength, folding resistance, excellent moisture resistance and stiffness, and excellent quality.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a modified polyvinyl alcohol is benzoyl oxidized paeoniflorin modified polyvinyl alcohol.
According to the invention, benzoyl oxidized paeoniflorin modified polyvinyl alcohol is adopted, and the benzoyl oxidized paeoniflorin modified polyvinyl alcohol and polyvinyl alcohol molecules form interaction for blending modification, and hydroxyl groups contained in benzoyl oxidized paeoniflorin are possibly used as hydrogen bonds to be combined with the polyvinyl alcohol, so that benzoyl oxidized paeoniflorin is possibly combined between the polyvinyl alcohol molecules at multiple points to introduce hydrophobic groups, and further the hydrophobicity of the polyvinyl alcohol is improved, the water absorption of the polyvinyl alcohol is reduced, and the polyvinyl alcohol has excellent moisture resistance; the compound is compounded with urea, paraformaldehyde and low-carbon alcohol to prepare the moisture absorption strength retaining agent for the corrugated case, and the moisture absorption strength retaining agent is applied to the corrugated case, so that the ring crush strength of the corrugated case is improved, the moisture resistance of the corrugated case is improved, the corrugated case still has higher ring crush strength in a humid environment, and the corrugated case treated by the surface sizing agent containing the retaining agent has stronger folding resistance, is not easy to bend and damage, and has excellent stiffness, so that the corrugated case with excellent quality is obtained.
Preferably, the weight ratio of the benzoyl oxidized paeoniflorin to the polyvinyl alcohol is 1: 4-10.
Preferably, the preparation method of the modified polyvinyl alcohol comprises the following steps:
dissolving polyvinyl alcohol in deionized water, swelling for 2-4 h at room temperature, and then heating to 90-95 ℃ to dissolve the polyvinyl alcohol, wherein the concentration of the polyvinyl alcohol is 10-15 wt%; dissolving benzoyl oxidized paeoniflorin in ethanol until the benzoyl oxidized paeoniflorin is completely dissolved, so that the concentration of the benzoyl oxidized paeoniflorin is 0.3-0.8 wt%; adding a benzoyl oxidized paeoniflorin solution into a polyvinyl alcohol solution, wherein the weight ratio of benzoyl oxidized paeoniflorin to polyvinyl alcohol is 1: 4-10, controlling the temperature to be 90-95 ℃, stirring and refluxing, reacting for 2.5-4.5 h, cooling to room temperature, and drying to obtain the modified polyvinyl alcohol.
The invention also discloses application of the benzoyl oxidized paeoniflorin in improving hydrophobicity of the modified polyvinyl alcohol.
The invention also discloses the application of the modified polyvinyl alcohol in the retention agent for the moisture absorption strength of the corrugated case.
The invention also discloses a moisture absorption strength maintaining agent for the corrugated case, which comprises the following components: modified polyvinyl alcohol, urea, paraformaldehyde, low-carbon alcohol, sodium hydroxide, an aldehyde capturing agent, a dispersion medium and a pH regulator.
Preferably, the modified polyvinyl alcohol is 2-6 parts by weight, the urea is 10-20 parts by weight, the paraformaldehyde is 4-12 parts by weight, the low-carbon alcohol is 5-10 parts by weight, the sodium hydroxide is 1-3 parts by weight, the aldehyde capturing agent is 1-3 parts by weight, the pH regulator is 1-4 parts by weight, and the dispersion medium is 45-75 parts by weight.
The invention also discloses a preparation method of the moisture absorption strength retention agent for the corrugated case.
A preparation method of a moisture absorption strength retention agent for corrugated cases comprises the following steps:
adding modified polyvinyl alcohol, urea, paraformaldehyde, low-carbon alcohol and sodium hydroxide into a dispersion medium, and uniformly stirring and mixing to obtain a mixed material;
and heating the mixed material to 85-100 ℃, adding an aldehyde capturing agent, continuing stirring for 1-3 h, cooling to room temperature, adding a pH regulator to regulate the pH value, and thus obtaining the moisture absorption strength maintaining agent for the corrugated case.
Preferably, the stirring speed is 250-500 r/min, and the stirring time is 15-30 min.
Preferably, the lower alcohol is one or more of lower mixed alcohol, ethanol or ethylene glycol.
Preferably, the dispersion medium is one of water and absolute ethyl alcohol.
Preferably, the pH of the moisture absorption strength maintaining agent for the corrugated case is 5.0-6.2.
The invention also discloses the application of the moisture absorption strength maintaining agent for the corrugated case in improving the ring crush strength of the corrugated case.
The invention adopts benzoyl oxidized paeoniflorin modified polyvinyl alcohol as the component of the moisture absorption strength maintaining agent of the corrugated case and treats the corrugated case, thereby having the following beneficial effects: the modified polyvinyl alcohol has excellent hydrophobicity, and is used in a retention agent to treat a corrugated case, so that the ring crush strength of the corrugated case is improved, and meanwhile, the moisture resistance of the corrugated case is improved, and the corrugated case still has higher ring crush strength in a humid environment; in addition, the corrugated case treated by the surface sizing solution containing the retention agent has higher folding endurance, so that the corrugated case is not easy to bend and break and has excellent stiffness. Therefore, the modified polyvinyl alcohol with certain hydrophobic property is used as a component of a moisture absorption strength retaining agent of the corrugated case in the corrugated case, so that the corrugated case has higher ring crush strength and folding endurance, and has excellent moisture resistance and stiffness, and the corrugated case with excellent quality is obtained.
Drawings
FIG. 1 is an infrared spectrum of polyvinyl alcohol before and after modification in example 2;
FIG. 2 is a water contact angle of polyvinyl alcohol before and after modification;
fig. 3 shows the breaking length of the corrugated box;
FIG. 4 is a ring crush index of a corrugated box;
fig. 5 is a folding endurance of the corrugated box;
fig. 6 shows the stiffness of the corrugated box.
Detailed Description
The raw materials used in this experimental example were purchased from:
polyvinyl alcohol: shanxi dish dragon assist sea medicine Limited company, the content is more than or equal to 99 percent; urea: suzhou Tailang chemical environmental protection science and technology limited, the content is more than or equal to 52 percent; paraformaldehyde: jinan Yingxin chemical Limited, the content is more than or equal to 96 percent; benzoyl oxidized paeoniflorin: the content of the product is more than or equal to 98 percent.
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1
A preparation method of modified polyvinyl alcohol comprises the following steps:
dissolving polyvinyl alcohol in deionized water, swelling for 2.5h at room temperature, and heating to 90 ℃ to dissolve the polyvinyl alcohol, wherein the concentration of the polyvinyl alcohol is 12.5 wt%; dissolving benzoyl oxidized paeoniflorin in ethanol until the benzoyl oxidized paeoniflorin is completely dissolved, so that the concentration of the benzoyl oxidized paeoniflorin is 0.55 wt%; adding the benzoyl oxidized paeoniflorin solution into the polyvinyl alcohol solution, wherein the weight ratio of the benzoyl oxidized paeoniflorin to the polyvinyl alcohol is 1:6, controlling the temperature at 90 ℃, stirring and refluxing, reacting for 3h, cooling to room temperature, and drying to obtain the modified polyvinyl alcohol.
Example 2
A preparation method of modified polyvinyl alcohol comprises the following steps:
dissolving polyvinyl alcohol in deionized water, swelling for 3.5h at room temperature, and heating to 93 ℃ to dissolve the polyvinyl alcohol, wherein the concentration of the polyvinyl alcohol is 13.7 wt%; dissolving benzoyl oxidized paeoniflorin in ethanol until the benzoyl oxidized paeoniflorin is completely dissolved, so that the concentration of the benzoyl oxidized paeoniflorin is 0.64 wt%; adding the benzoyl oxidized paeoniflorin solution into the polyvinyl alcohol solution, wherein the weight ratio of the benzoyl oxidized paeoniflorin to the polyvinyl alcohol is 1:8, controlling the temperature at 93 ℃, stirring and refluxing, reacting for 4 hours, cooling to room temperature, and drying to obtain the modified polyvinyl alcohol.
Example 3
A preparation method of modified polyvinyl alcohol comprises the following steps:
dissolving polyvinyl alcohol in deionized water, swelling for 3 hours at room temperature, and then heating the solution to 95 ℃ for dissolving, wherein the concentration of the polyvinyl alcohol is 15 wt%; dissolving benzoyl oxidized paeoniflorin in ethanol until the benzoyl oxidized paeoniflorin is completely dissolved, so that the concentration of the benzoyl oxidized paeoniflorin is 0.35 wt%; adding the benzoyl oxidized paeoniflorin solution into the polyvinyl alcohol solution, wherein the weight ratio of the benzoyl oxidized paeoniflorin to the polyvinyl alcohol is 1:10, controlling the temperature at 95 ℃, stirring and refluxing, reacting for 2.5h, cooling to room temperature, and drying to obtain the modified polyvinyl alcohol.
Example 4
A preparation method of a moisture absorption strength retention agent for corrugated cases comprises the following steps:
adding 3 parts by weight of the modified polyvinyl alcohol in example 1, 12 parts by weight of urea, 8 parts by weight of paraformaldehyde, 5 parts by weight of ethylene glycol and 1 part by weight of sodium hydroxide into 50 parts by weight of ethanol, stirring at a stirring speed of 300r/min for 20min, and uniformly mixing to obtain a mixed material;
and heating the mixed material to 90 ℃, adding 1.5 parts by weight of aldehyde capturing agent, continuing stirring for 2 hours, cooling to room temperature, adding hydrochloric acid to adjust the pH value to 5.6, and obtaining the moisture absorption strength maintaining agent for the corrugated case.
Example 5
A preparation method of a moisture absorption strength retention agent for corrugated cases comprises the following steps:
adding 6 parts by weight of the modified polyvinyl alcohol in example 1, 17 parts by weight of urea, 11 parts by weight of paraformaldehyde, 7 parts by weight of ethylene glycol and 2 parts by weight of sodium hydroxide into 75 parts by weight of ethanol, stirring at a stirring rate of 500r/min for 15min, and uniformly mixing to obtain a mixed material;
and heating the mixed material to 95 ℃, adding 3 parts by weight of aldehyde capturing agent, continuing stirring for 2 hours, cooling to room temperature, adding hydrochloric acid to adjust the pH value to 5.9, and obtaining the moisture absorption strength maintaining agent for the corrugated case.
Example 6
The other steps of the preparation method of the moisture absorption strength retention agent for the corrugated case are the same as those of the embodiment 4, and are different from the embodiment 4 in that:
according to the parts by weight, 3 parts by weight of the modified polyvinyl alcohol in the example 2, 12 parts by weight of urea, 8 parts by weight of paraformaldehyde, 5 parts by weight of ethylene glycol and 1 part by weight of sodium hydroxide are added into 50 parts by weight of ethanol, stirred for 20min at the stirring speed of 300r/min, and mixed uniformly to obtain a mixed material.
Example 7
The other steps of the preparation method of the moisture absorption strength retention agent for the corrugated case are the same as those of the embodiment 4, and are different from the embodiment 4 in that:
according to the parts by weight, 3 parts by weight of the modified polyvinyl alcohol in example 3, 12 parts by weight of urea, 8 parts by weight of paraformaldehyde, 5 parts by weight of ethylene glycol and 1 part by weight of sodium hydroxide are added into 50 parts by weight of ethanol and stirred for 20min at the stirring speed of 300r/min, and the mixture is uniformly mixed to obtain a mixed material.
Example 8
In order to further improve the moisture resistance of the moisture absorption strength retention agent for corrugated cases and enable the corrugated cases treated by the retention agent to have better tensile strength and long fracture length, the preferable measures further comprise:
0.5-1.5 parts by weight of dipropylene glycol methyl ether acetate is added into the moisture-absorption strength retention agent for the corrugated case, and the dipropylene glycol methyl ether acetate and the modified polyvinyl alcohol are further coupled among molecules, so that a better network structure can be formed, the moisture resistance of the moisture-absorption strength retention agent for the corrugated case is further improved, and the moisture resistance of the corrugated case is further improved by applying the strength retention agent to the corrugated case, and the corrugated case has better tensile strength and long fracture length. The specific implementation mode is as follows:
the other steps of the preparation method of the moisture absorption strength retention agent for the corrugated case are the same as those of the embodiment 6, and are different from the embodiment 6 in that:
according to the parts by weight, 3 parts by weight of the modified polyvinyl alcohol in the example 2, 12 parts by weight of urea, 8 parts by weight of paraformaldehyde, 5 parts by weight of ethylene glycol, 1 part by weight of sodium hydroxide and 1.1 part by weight of dipropylene glycol methyl ether acetate are added into 50 parts by weight of ethanol and stirred for 20min at the stirring speed of 300r/min, and the mixture is uniformly mixed to obtain a mixed material.
Example 9
The other steps of the preparation method of the moisture absorption strength retention agent for the corrugated case are the same as those of the embodiment 6, and are different from the embodiment 6 in that:
according to the parts by weight, 3 parts by weight of the modified polyvinyl alcohol in the example 2, 12 parts by weight of urea, 8 parts by weight of paraformaldehyde, 5 parts by weight of ethylene glycol, 1 part by weight of sodium hydroxide and 1.5 parts by weight of dipropylene glycol methyl ether acetate are added into 50 parts by weight of ethanol and stirred for 20min at the stirring speed of 300r/min, and the mixture is uniformly mixed to obtain a mixed material.
Example 10
The other steps of the preparation method of the moisture absorption strength retention agent for the corrugated case are the same as those of the embodiment 8, and are different from the embodiment 8 in that:
according to the parts by weight, 3 parts by weight of polyvinyl alcohol, 12 parts by weight of urea, 8 parts by weight of paraformaldehyde, 5 parts by weight of ethylene glycol, 1 part by weight of sodium hydroxide and 1.1 part by weight of dipropylene glycol methyl ether acetate are added into 50 parts by weight of ethanol and stirred for 20min at the stirring speed of 300r/min, and the mixture is uniformly mixed to obtain a mixed material.
Comparative example 1
The other steps of the preparation method of the moisture absorption strength retention agent for the corrugated case are the same as those of the embodiment 6, and are different from the embodiment 6 in that:
according to the parts by weight, 3 parts by weight of polyvinyl alcohol, 12 parts by weight of urea, 8 parts by weight of paraformaldehyde, 5 parts by weight of ethylene glycol and 1 part by weight of sodium hydroxide are added into 50 parts by weight of ethanol and stirred for 20min at the stirring speed of 300r/min, and the mixture is uniformly mixed to obtain a mixed material.
Test example 1
1. Determination of modified polyvinyl alcohol infrared spectrogram
The test adopts a NEXUS-670 infrared spectrometer of American Nicolet company; the test range is 4000-500cm-1Scan 10 times.
FIG. 1 is an infrared spectrum of polyvinyl alcohol before and after modification in example 2. As can be seen from FIG. 1, the infrared spectrum of the unmodified polyvinyl alcohol was 3394cm-1The characteristic absorption peak appearing nearby is the stretching vibration of O-H in polyvinyl alcohol; at 1337cm-1The nearby characteristic absorption peak is the bending vibration of CH-OH; the infrared spectrum of the modified polyvinyl alcohol is 3613cm relative to that of the unmodified polyvinyl alcohol-1The characteristic absorption peak of O-H appeared nearby shifts to high wave number, which is probably caused by hydrogen bond formed between hydroxyl in benzoyl oxidized paeoniflorin and polyvinyl alcohol molecules; at 1761cm-1The characteristic absorption peak appeared nearby is C = O stretching vibration in ArCOOR, and is 813cm-1The characteristic absorption peak appearing nearby is the stretching vibration of the six-membered monoepoxy cyclic ether; thus, it can be seen that the use of benzoyl oxidized paeoniflorin to polyvinyl alcohol yields modified polyvinyl alcohol.
2. Measurement of contact Angle of modified polyvinyl alcohol
OCA-40 contact angle measuring instrument of Germany Datophysics was used. Testing the contact angle of water on the surface of the sample; unmodified polyvinyl alcohol was used as a control; the test temperature was 20. + -. 0.3 ℃ and 3 replicates were taken and the mean value was taken.
FIG. 2 shows the water contact angle of polyvinyl alcohol before and after modification. Curves a, b, c and d represent the change curves of the water contact angles of the example 2, the example 3 and the example 1, respectively, and the control group along with the increase of time; as can be seen from FIG. 2, examples 1-3 exhibited better hydrophobicity with water contact angle higher than 105 ° at 0 s; the water contact angle shows a decreasing trend with increasing time, and reaches equilibrium after 3s, and the water contact angle is higher than 83 degrees; in example 2, when the equilibrium is reached, the water contact angle is still higher than 90 degrees, and the water-repellent coating has certain hydrophobicity; comparing examples 1-3 with the control, examples 1-3 had significantly higher water contact angles than the control; this shows that the benzoyl oxidized paeoniflorin is adopted to modify the polyvinyl alcohol, so that the water contact angle of the polyvinyl alcohol is improved, and the modified polyvinyl alcohol with certain hydrophobic property is obtained.
Test example 2
The holding agents prepared in examples 4 to 10 and comparative example 1 were applied to a surface sizing solution (sizing starch) in a weight ratio of 5:95, as an example of a 170-gram corrugated cardboard box, and then the surface sizing solution was used as a blank without adding the holding agent.
1. Determination of tensile Strength and breaking Length of corrugated cardboard
Cutting the measured paper sample into strips with width of 10mm after constant humidity for 4h, selecting out a sample with length of more than 130mm for detecting tensile strength, and quantitatively measuring the tensile index with a DZ-5000 type paper tensile testing machine, wherein the unit is N.m.g-1。
The calculation formula of the fracture length is as follows:
Lb=(S×103)/(9.8·g)
in the formula: l isbKm for fracture length; s is tensile strength, KN/m; g is quantitative, g/m2。
Fig. 3 shows the breaking length of the corrugated box. As can be seen from fig. 3, the breaking length of examples 4 to 7 was higher than 7.75km, the breaking length of comparative example 6 was higher than that of comparative example 1, and example 6 was higher than that of comparative example 1, which illustrates that modifying polyvinyl alcohol with benzoyloxypaeoniflorin and applying the modified polyvinyl alcohol as an ingredient of a holding agent to the surface of a corrugated case, which improves the tensile strength of the corrugated case having a higher breaking length; comparing example 6 with examples 8 to 9, and example 10 with comparative example 1, the fracture length of examples 8 to 9 was higher than that of example 6, and the fracture length of example 10 was higher than that of comparative example 1, which shows that the tensile strength and the fracture length of the corrugated case were further improved by adding dipropylene glycol methyl ether acetate to the holding agent. Comparing examples 1-10, comparative example 1 and blank group, the fracture length of examples 1-10 and comparative example 1 is higher than that of blank group, which shows that the retention agent prepared by the technical scheme is added into the surface sizing solution to improve the tensile strength and fracture length of the corrugated case to a certain extent.
2. Determination of ring crush strength of corrugated paper box
The ring crush strength of corrugated containers was measured according to GB/T2679.8-1995.
Fig. 4 is a ring crush index of the corrugated box. As can be seen from FIG. 4, the ring pressure index of examples 4 to 7 was higher than 15.6 N.m.g-1After moisture absorption, the ring pressure index is still higher than 15.45 Nm.g-1The variation of the ring pressure index is less than 0.17 Nm.g-1In examples 8 to 9, the ring pressure index after moisture absorption was still higher than 15.95 Nm g-1The variation of the ring pressure index is less than 0.1 Nm.g-1(ii) a Comparing example 6 with comparative example 1, the ring crush indexes before and after moisture absorption of example 6 are all higher than those of comparative example 1, which shows that the ring crush strength of the corrugated case is improved by modifying polyvinyl alcohol with benzoyl oxidized paeoniflorin and applying the modified polyvinyl alcohol as a component of a retention agent to the surface of the corrugated case, and the corrugated case has excellent moisture resistance, so that the corrugated case still keeps good ring crush strength after moisture absorption in a humid environment; comparing example 6 with examples 8 to 9, and example 10 with comparative example 1, the ring crush indexes of examples 8 to 9 and example 6 before moisture absorption are not obviously different, and the ring crush indexes of example 10 and comparative example 1 before moisture absorption are also not obviously different, while after moisture absorption, the variation of the ring crush indexes of examples 8 to 9 is lower than that of example 6, and the variation of the ring crush index of example 10 is lower than that of comparative example 1, which shows that the addition of dipropylene glycol methyl ether acetate in the retention agent has no obvious influence on the ring crush strength of the corrugated case, but has a certain improvement on the moisture resistance of the corrugated case. Comparing examples 1-10, comparative example 1 and blank group, the ring crush indexes before and after moisture absorption of examples 1-10 and comparative example 1 are all higher than that of the blank group, and the ring crush strength and the anti-blocking performance of the corrugated case by adding the retention agent prepared by the technical scheme into the surface sizing solution are illustratedThe moisture performance is also improved to a certain extent.
3. Measurement of folding resistance of corrugated cardboard box
Samples are collected and processed according to the standard, and experiments are carried out under the standard atmospheric condition; at least 10 test pieces with width (10 +/-0.2) mm and length 150mm are cut in the longitudinal direction and the transverse direction respectively. The sample is placed between the sample and the chuck, the sample is folded back and forth in a certain angle through the left-right swing of the chuck under certain tension, the strength of the sample is gradually reduced along with the increase of the folding times until the sample cannot bear the tension of the spring, and the folding times during the fracture are the folding resistance of the sample.
Fig. 5 shows the folding endurance of the corrugated cardboard box. As can be seen from fig. 5, the folding endurance of examples 4 to 7 is not less than 20 times, the folding endurance of comparative example 6 and comparative example 1, and the folding endurance of example 6 is higher than that of comparative example 1, which shows that the modification of polyvinyl alcohol by benzoyl oxidized paeoniflorin and the application of the modified polyvinyl alcohol as a component of a retention agent to the surface of a corrugated case improve the folding endurance of the corrugated case and reach or exceed the grade a index of the national standard; comparing example 6 with examples 8 to 9, and example 10 with comparative example 1, the folding endurance of examples 8 to 9 was almost the same as that of example 6, and the folding endurance of example 10 was also almost the same as that of comparative example 1, which indicates that the addition of dipropylene glycol methyl ether acetate to the holding agent had no significant effect on the folding endurance of the corrugated cardboard box. Comparing examples 1-10, comparative example 1 and blank group, the folding endurance of examples 1-10 and comparative example 1 is higher than that of blank group, which shows that the folding endurance of corrugated case is improved by adding the retention agent prepared by the technical scheme into the surface sizing solution.
4. Measurement of stiffness of corrugated cardboard box
The stiffness of the corrugated case is measured according to GB/T2679.3-1996; mN (bending force).
Fig. 6 shows the stiffness of the corrugated box. As can be seen from fig. 6, the stiffness of examples 4 to 7 was higher than 27mN, the stiffness of comparative example 6 and comparative example 1, and example 6 was higher than comparative example 1, which illustrates that modifying polyvinyl alcohol with benzoyloxypaeoniflorin and applying the modified polyvinyl alcohol as a component of a retention agent to the surface of a corrugated case, which improves the stiffness of the corrugated case; comparing example 6 with examples 8 to 9, and example 10 with comparative example 1, the stiffness of examples 8 to 9 was not significantly different from example 6, and was slightly improved, and the stiffness of example 10 was also not significantly different from comparative example 1, which indicates that the addition of dipropylene glycol methyl ether acetate to the retention agent did not significantly affect the stiffness of the corrugated case. Comparing examples 1-10, comparative example 1 and blank group, the folding endurance of examples 1-10 and comparative example 1 is higher than that of blank group, which shows that the retention agent prepared by adding the technical scheme into the surface sizing solution has little influence on the stiffness of the corrugated case.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art and will not be described herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A modified polyvinyl alcohol is benzoyl oxidized paeoniflorin modified polyvinyl alcohol.
2. A modified polyvinyl alcohol according to claim 1, wherein: the weight ratio of the benzoyl oxidized paeoniflorin to the polyvinyl alcohol is 1: 4-10.
3. The application of benzoyl oxidized paeoniflorin in improving the hydrophobicity of modified polyvinyl alcohol.
4. Use of the modified polyvinyl alcohol of claim 1 in a retention agent for moisture absorption strength of corrugated containers.
5. A moisture absorption strength retaining agent for corrugated cases, comprising: the modified polyvinyl alcohol according to claim 1, urea, paraformaldehyde, a lower alcohol, sodium hydroxide, an aldehyde capturing agent, a dispersion medium, and a pH adjusting agent.
6. The moisture absorption strength retaining agent for corrugated containers as claimed in claim 5, wherein: the modified polyvinyl alcohol is 2-6 parts by weight, the urea is 10-20 parts by weight, the paraformaldehyde is 4-12 parts by weight, the low-carbon alcohol is 5-10 parts by weight, the sodium hydroxide is 1-3 parts by weight, the aldehyde capturing agent is 1-3 parts by weight, the pH regulator is 1-4 parts by weight, and the dispersion medium is 45-75 parts by weight.
7. The method for preparing a retention agent for moisture absorption strength of corrugated containers as claimed in claim 5, comprising the steps of:
adding modified polyvinyl alcohol, urea, paraformaldehyde, low-carbon alcohol and sodium hydroxide into a dispersion medium, and uniformly stirring and mixing to obtain a mixed material;
and heating the mixed material to 85-100 ℃, adding an aldehyde capturing agent, continuing stirring for 1-3 h, cooling to room temperature, adding a pH regulator to regulate the pH value, and thus obtaining the moisture absorption strength maintaining agent for the corrugated case.
8. The method for producing a retention agent for moisture absorption strength of a corrugated box according to claim 7, wherein: the dispersion medium is one of water and absolute ethyl alcohol.
9. The method for producing a retention agent for moisture absorption strength of a corrugated box according to claim 7, wherein: the pH value of the moisture absorption strength maintaining agent for the corrugated case is 5.0-6.2.
10. Use of the moisture absorption strength maintaining agent for corrugated containers according to claim 5 for increasing the ring crush strength of corrugated containers.
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