CN105542676B - It is a kind of using nano oxidized cellulose slurries as starch adhesive of parent and preparation method thereof - Google Patents

Abstract

The invention discloses a starch adhesive based on nano-oxidized cellulose slurry, which comprises the following raw materials in parts by weight: 100 parts of oxidized nano-cellulose slurry with an oxidation rate of 5% to 30%, 10-30% nano-oxidized cellulose slurry, 40 parts of starch, 2 to 5 parts of oxidizing agent, 0.1 to 2 parts of stabilizer, 0.1 to 2 parts of preservative and 0.1 to 2 parts of emulsified paraffin. The preparation method of the present invention: first prepare the nano-oxidized cellulose slurry with an oxidation rate of 5% to 30%, then add starch and 2 to 5 oxidants in batches to the prepared nano-oxidized cellulose slurry, and then add the stabilizer after fully stirring , preservative and emulsified paraffin, fully stirred at 50-70°C until the components are uniformly dispersed, and the starch adhesive is obtained. The starch adhesive of the invention has high bonding strength and good water resistance. The preparation method of the invention avoids solvent replacement and drying process, greatly reduces energy consumption and labor intensity.

Description

A starch adhesive based on nano-oxidized cellulose slurry and its preparation method

technical field

The invention relates to an adhesive and a preparation method thereof, in particular to a starch adhesive with nano-oxidized cellulose slurry as a matrix and a preparation method thereof.

Background technique

With the promulgation of environmental protection laws and the enhancement of people's health awareness, the state has become more and more strict on the volatilization of free formaldehyde in acetal adhesives. The "trialdehyde glue" (urea-formaldehyde resin, phenolic resin and melamine-formaldehyde resin adhesive) commonly used in the field of wood processing at present releases a large amount of formaldehyde in the process of production and use, causing environmental pollution and endangering public health. Therefore, the development of non-toxic and environmentally friendly wood adhesives will be the focus of future research.

Starch adhesive, as an environment-friendly natural adhesive, has attracted more and more attention from researchers. Starch has become the wood with the most development potential due to its advantages of abundant resources, low price, convenient use, etc., as well as its non-toxic and environmental protection. Use one of the natural adhesives. However, starch glue also has its limitations. The adhesive strength and water resistance of starch glue are not good. In order to prepare starch glue with good properties, some methods have been disclosed so far. In the Chinese Invention Patent Application Publication (publication number: CN101760148A), it is proposed to enhance the coating performance and strength of cornstarch through oxidation reaction. In the Chinese Invention Patent Application Publication (publication number: CN 104817981 A), it is proposed to add borax, sodium stearate, tributyl phosphate and nano _- SiO sol to the starch to improve the adhesiveness due to the interaction of each component. strength.

In recent years, nanocellulose has attracted a lot of attention as a new type of renewable nanomaterial. The diameter of nanocellulose is about 1nm to 100nm, and it can be dispersed in water to form a stable colloid. It not only has the basic structure and performance of cellulose, but also has the characteristics of nanoparticles, and has good macroscopic quantum tunnel size effect, surface effect and quantum size effect. Because of its unique properties, nanocrystalline cellulose is widely used in papermaking, textile, It is widely used in fine chemical industry and other fields. There are also relevant studies on the corresponding properties of adhesives enhanced by using nanocellulose as an additive. In the Chinese Invention Patent Application Publication (publication number: CN 103013436 A), it is proposed to use nanocellulose as a modifier to enhance the adhesive strength of soybean protein. In the Chinese Invention Patent Application Publication (Publication No.: CN 103266536 A), it is proposed to add nano-microcrystalline cellulose colloid prepared from microcrystalline cellulose powder to gelatinized cationic starch glue to prepare a high-strength , Surface sizing agent with good stability. By adding nano-microcrystalline cellulose modified starch glue to obtain better adhesive strength or water resistance, but there are still some things that can be improved. As mentioned above, in the preparation process of nanocellulose modified starch glue, the microcrystalline nanocellulose powder prepared earlier is used as raw material. Slurry contains a large amount of solvent, and the process of concentrating and drying it needs to consume a lot of energy; on the other hand, the drying process of using plant fibers to prepare microcrystalline nanocellulose has a greater impact on the morphology and properties of nanofibers , causing the reduction of its quantum size effect, adding it to starch glue has a limited effect on enhancing the adhesive strength.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art, provide a starch adhesive with good water resistance and high adhesive strength, which uses nano-oxidized cellulose slurry as the matrix, and a starch adhesive with low energy consumption and simple steps. The invention discloses a preparation method of a starch adhesive with nano-oxidized cellulose slurry as a matrix.

In order to solve the problems of the technologies described above, the technical solution proposed by the present invention is:

A starch adhesive based on nano-oxidized cellulose slurry, in parts by weight, comprising the raw materials of the following components:

100 parts of nano oxidized cellulose slurry with an oxidation rate of 5% to 30%, 10 to 40 parts of starch, 2 to 5 parts of oxidizing agent, 0.1 to 2 parts of stabilizer, 0.1 to 2 parts of preservative and 0.1 to 2 parts of emulsified paraffin. Wherein the oxidation rate is the percentage of the number of oxidized hydroxyl groups in the nanocellulose to the total number of hydroxyl groups, and the nano-oxidized cellulose and unoxidized nano-cellulose form a certain ratio to strengthen the starch adhesive.

For the above-mentioned starch adhesive, preferably, the solid content of the nano-oxidized cellulose slurry is 8% to 12%.

For the aforementioned starch adhesive, preferably, the mass fraction of oxidized cellulose with a fiber length of 1 to 100 nm in the nano-oxidized cellulose slurry is 35% to 70%; the mass fraction of oxidized cellulose with a fiber length of 100 to 1000 nm is 20% to 50%; the mass fraction of oxidized cellulose with a fiber length of 1 μm to 10 mm is 10% to 15%.

For the above starch adhesive, preferably, the oxidant is H ₂ O ₂ or/and NaClO; the stabilizer is polyethylene glycol; and the preservative is ammonium pentaborate.

As a general inventive concept, the present invention also provides a method for preparing starch glue based on nano-oxidized cellulose slurry, comprising the following steps:

(1) Take 8-12 parts of pulp board, add it to 80-100 parts of sulfuric acid solution, shear and stir at 50-55°C for 1-3 hours, then add 1-2 parts of oxidant to continue shearing and stirring for 0.5- 1.0h; finally add 200-1000 parts of water to terminate the reaction, dialyze the obtained product to a nano-oxidized cellulose slurry with a pH of 1-5 and an oxidation rate of 5%-30%;

(2) Take 100 parts of nano-oxidized cellulose slurry obtained in step (1), add 10-40 parts of starch and 2-5 parts of oxidizing agent in batches, and then add 0.1-2 parts of stabilizer, 0.1-2 parts of The preservative and 0.1-2 parts of emulsified paraffin are fully stirred at 50-70° C. until the components are uniformly dispersed, and the starch adhesive based on nano-oxidized cellulose slurry is obtained.

In the above-mentioned preparation method, preferably, in the step (2), the specific steps of adding starch and oxidant in batches are: adding 5% to 10% of the starch mass and 10% to 10% of the oxidant mass in the proportioning ratio for the first time 15%, fully stir the gelatinization reaction at 50-70°C for 0.5-1h; add 30-40% of the starch mass and 40%-50% of the oxidant mass in the ratio for the second time, and fully stir at 50-70°C 0.5-1h; add 50%-65% of the starch mass and 35%-50% of the oxidant mass in the proportioning for the third time, and fully stir at 50-70°C for 0.5-1h.

In the above preparation method, preferably, the solid content of the nano-oxidized cellulose slurry obtained in the step (1) is 8% to 12%; The fraction is 35%-70%; the mass fraction of oxidized cellulose with a fiber length of 100-1000nm is 20%-50%; the mass fraction of oxidized cellulose with a fiber length of 1 μm-10mm is 10%-15%.

In the above preparation method, preferably, the oxidant H ₂ O ₂ or/and NaClO; the stabilizer is polyethylene glycol; and the preservative is ammonium pentaborate.

In the above preparation method, preferably, in the step (1), the mass concentration of the sulfuric acid solution is 20%-60%; the shear rate is 2000-5000rpm.

Through the above steps (1), a nano-oxidized cellulose slurry with an oxidation rate of 5% to 30% is obtained. In the subsequent step (2), the nano-cellulose is further oxidized, and the nano-oxidized cellulose in the finally obtained adhesive is oxidized The rate is 10% to 50%.

The present invention is based on the formation of uronic acid groups and carboxyl groups after the partial oxidation reaction of nanocellulose. As shown in formula (1), nano-oxidized cellulose can utilize uronic acid groups and carboxyl groups and starch to form a strong and effective Cross-linking, which is beneficial to improve the bonding strength and water resistance of the adhesive.

Compared with the prior art, the present invention has the advantages of:

(1) The present invention directly uses nano-oxidized cellulose slurry as a matrix to prepare nano-cellulose-reinforced starch adhesive, which avoids the solvent replacement and drying process in the preparation of nano-cellulose, greatly reduces energy consumption, and reduces labor intensity; At the same time, retaining part of the sulfuric acid in the preparation of nanocellulose as a catalyst in the starch oxidation process can effectively save resources and reduce pollution.

(2) The present invention adopts the combination of sulfuric acid hydrolysis and mechanical shearing to prepare the nano-oxidized cellulose slurry with a certain length distribution as matrix reinforced starch glue, which can not only fully retain the quantum size effect of nano-cellulose, but also give full play to different lengths. The reinforcing effect of nanocellulose guarantees its enhancing effect on adhesive strength.

(3) The present invention adopts nano-cellulose reinforcement, and the combination of nano-oxidized cellulose and oxidized starch can effectively improve the compatibility and binding strength of cellulose and starch.

(4) In the present invention, starch is added in batches to the nano-oxidized cellulose slurry, and it is oxidized with an appropriate oxidizing agent. Through the technical combination of these two items, the aggregation and coagulation of starch in the slurry are effectively prevented, and the starch concentration is improved. Adhesive stability.

(5) the present invention has carried out sufficient emulsification to nano-oxidized cellulose after adding starch in batches and carries out gelatinization reaction, has increased the stability and the wet strength of starch adhesive, and the addition of emulsified paraffin is also conducive to the formation of suitable surface layers The hydrophobic layer enhances the water resistance of the starch adhesive. On the one hand, the stabilizer polyvinyl alcohol can effectively prolong the storage period of the adhesive. This is because the polyvinyl alcohol molecule contains hydrophilic and hydrophobic groups, which can act as a protective colloid after being dissolved in water and wrap on the surface of starch granules. , to shield the hydroxyl groups between the particles and stabilize the dispersion system. On the other hand, the polyvinyl alcohol disperses the starch particles evenly, effectively preventing the agglomeration and coagulation of the starch in the slurry, and improving the stability of the starch adhesive. The preservative ammonium pentaborate has antiseptic effect, and at the same time, this molecule is also conducive to dispersing starch granules and improving system stability. The components cooperate with each other to produce a composite synergistic effect and effectively improve the stability of the starch adhesive.

(6) The starch adhesive prepared by using the nano-oxidized cellulose slurry with an oxidation rate of 5% to 30% as a matrix in the present invention has the advantages of high bonding strength and good water resistance.

detailed description

In order to facilitate the understanding of the present invention, the following will describe the present invention more fully and in detail in combination with preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.

Unless otherwise defined, all technical terms used hereinafter have the same meanings as commonly understood by those skilled in the art. The terminology used herein is only for the purpose of describing specific embodiments, and is not intended to limit the protection scope of the present invention.

Unless otherwise specified, the various reagents and raw materials used in the present invention are commercially available products or products that can be prepared by known methods.

Example 1:

A starch adhesive based on nano-oxidized cellulose slurry of the present invention, comprising the raw materials of the following components: 100 grams of oxidized cellulose slurry (solid content 8%) with an oxidation rate of 10%, 10 grams of starch, 2 The gram mass concentration is 30% oxidant H ₂ O ₂ , 0.2 gram stabilizer polyvinyl alcohol, 0.1 gram antiseptic ammonium pentaborate and 1 gram emulsified paraffin; the nanofiber length in the nano-oxidized cellulose is 1-100 nm and the content is 40 %; the content of nanofibers with a length of 100-1000nm is 45%; the content of fibers with a length of 1 μm-10mm is 15%.

The preparation method of the starch adhesive based on the nano-oxidized cellulose slurry of the present embodiment comprises the following steps:

(1) Take 8 grams of pulp board, add 80 grams of mass concentration to 20% sulfuric acid solution, shear and stir for 1h at a temperature of 50°C (shear rate is 2000rpm), and then add 1 gram of mass concentration to be 30% Oxidant H ₂ O ₂ continued to shear and stir the reaction for 0.5h; finally, 300 grams of water was added to terminate the reaction, the obtained product was put into a dialysis bag, and dialyzed to pH = 5, the solid content was 8%, and the oxidation rate was 10%. Oxidized cellulose slurry; nanofiber length distribution in the nano-oxidized cellulose slurry: 1-100nm, 40%; 100-1000nm, 45%; 1 μm-10mm, 15%.

(2) Take 100 grams of nano-oxidized cellulose slurry obtained in step (1), add 10 grams of starch and 2 grams of oxidant H ₂ O ₂ with a mass concentration of 30% in batches, and add 0.5 gram of starch and 0.2 gram of oxidant for the first time Mass, fully stirred gelatinization reaction at 50°C for 0.5h; for the second time, 3g of starch and 0.8g of oxidant, fully stirred at 50°C for 0.5h; for the third time, add 6.5g of starch and 1g of oxidant, Stir well for 0.5h; then add 0.2g of stabilizer polyvinyl alcohol, 0.1g of preservative ammonium pentaborate and 1g of emulsified paraffin; stir well at 50°C until the components are evenly dispersed and fully reacted to obtain oxidized cellulose The slurry is the parent starch adhesive.

Sand the surface of the veneer with a moisture content of about 4.5% and a format of 300mm×300mm; apply the starch adhesive with the nano-oxidized cellulose slurry prepared in this example as the matrix evenly on the veneer with a sizing amount of 300g/ ^m2 Surface; then pre-press for 2 minutes under the pre-pressing machine; then perform hot-pressing under the conditions of hot-pressing 3MPa and hot-pressing time 1mm/min.

According to GB/T9846-2004 II class plywood standard, measure the plywood water resistance of the above-mentioned preparation; According to GB/T9846-2004 II class plywood standard, adopt tensile machine to measure (with reference to GB/T17657-1999 standard sample preparation) the bonding strength of plywood, the result As shown in Table 1.

Example 2:

A starch adhesive based on nano-oxidized cellulose slurry of the present invention, comprising the raw materials of the following components: 100 grams of oxidized cellulose slurry (solid content 10%) with an oxidation rate of 15%, 20 grams of starch, 5 Gram oxidant NaClO, 0.5 gram stabilizer polyvinyl alcohol, 0.2 gram preservative ammonium pentaborate and 0.5 gram emulsified paraffin; The nanofiber length in the nano-oxidized cellulose is 47% for the nanofiber length of 1～100nm; The nanofiber length is 100～ The content of 1000nm is 40%; the content of fiber length of 1 μm ~ 10mm is 13%.

The preparation method of the starch adhesive based on the nano-oxidized cellulose slurry of the present embodiment comprises the following steps:

(1) Take 10 grams of pulp board, add 90 grams of mass concentration to 40% sulfuric acid solution, shear and stir for 1 h (shear rate is 2000 rpm) at a temperature of 55 ° C, then add 1 gram of oxidant NaClO to continue shear and stir React for 1.0 h; finally add 500 grams of water to terminate the reaction, put the obtained product into a dialysis bag, and dialyze to a nano-oxidized cellulose slurry with a pH=4, a solid content of 10%, and an oxidation rate of 15%; the nano-oxidized fiber Nanofiber length distribution in plain slurry: 1-100nm, 47%; 100-1000nm, 40%; 1 μm-10mm, 13%.

(2) Take 100 grams of nano-oxidized cellulose slurry obtained in step (1), add 20 grams of starch and 5 grams of oxidizing agent NaClO in batches, add 2 grams of starch and 0.75 grams of oxidizing agent for the first time, and fully stir at 60 ° C Gelatinization reaction for 0.5h; for the second time, 8g of starch and 2.5g of oxidant, fully stirred at 60°C for 0.5h; for the third time, 10g of starch and 1.75g of oxidant were added, and fully stirred for 0.5h at 60°C; 0.5 g of stabilizer polyvinyl alcohol, 0.2 g of preservative ammonium pentaborate and 0.5 g of emulsified paraffin, fully stirred at 60 ° C until the components are evenly dispersed and fully reacted to obtain a starch adhesive based on nano-oxidized cellulose slurry. agent.

Sand the surface of the veneer with a moisture content of about 4.5% and a format of 300mm×300mm; apply the starch adhesive with the nano-oxidized cellulose slurry prepared in this example as the matrix evenly on the veneer with a sizing amount of 300g/ ^m2 Surface; then pre-press for 2 minutes under the pre-pressing machine; then perform hot-pressing under the conditions of hot-pressing 3MPa and hot-pressing time 1mm/min.

According to GB/T9846-2004 II class plywood standard, measure the plywood water resistance of the above-mentioned preparation; According to GB/T9846-2004 II class plywood standard, adopt tensile machine to measure (with reference to GB/T17657-1999 standard sample preparation) the bonding strength of plywood, the result As shown in Table 1.

Example 3:

A starch adhesive based on nano-oxidized cellulose slurry of the present invention, comprising the raw materials of the following components: 100 grams of oxidized cellulose slurry with an oxidation rate of 20% (solid content 12%), 30 grams of starch, 5 The gram mass concentration is 30% oxidant H ₂ O ₂ , 1 gram of stabilizer polyvinyl alcohol, 1 gram of preservative ammonium pentaborate and 1 gram of emulsified paraffin; the nanofiber length in the nano-oxidized cellulose is 1-100 nm and the content is 60 %; the content of nanofibers with a length of 100-1000nm is 35%; the content of fibers with a length of 1 μm-10mm is 10%.

The preparation method of the starch adhesive based on the nano-oxidized cellulose slurry of the present embodiment comprises the following steps:

(1) Take 10 grams of pulp board, add 90 grams of concentration into 50% sulfuric acid solution, shear and stir for 2 hours at a temperature of 55°C (shear rate is 4000rpm), then add 2 grams of oxidant with a mass concentration of 30% H ₂ O ₂ continued to shear and stir the reaction for 1.0h; finally, 600 grams of water was added to terminate the reaction, and the obtained product was put into a dialysis bag, and dialyzed to pH = 2, a solid content of 12%, and an oxidation rate of 20%. Cellulose slurry; the nanofiber length distribution in the nano-oxidized cellulose slurry: 1-100nm, 60%; 100-1000nm, 35%; 1 μm-10mm, 10%.

(2) Take 100 grams of nano-oxidized cellulose slurry obtained in step (1), add 30 grams of starch and 5 grams of oxidant H ₂ O ₂ with a mass concentration of 30% in batches, add 2.4 grams of starch and 0.75 grams of starch for the first time Quality of oxidant, fully stirred gelatinization reaction at 60°C for 0.5h; for the second time, 12g of starch and 2.25g of oxidant were fully stirred at 60°C for 0.5h; for the third time, 15.6g of starch and 2g of oxidant were added, Stir well at 60 °C for 0.5 h; then add 1 g of stabilizer polyvinyl alcohol, 1 g of preservative ammonium pentaborate, and 1 g of emulsified paraffin, and stir well at 60 ° C until the components are evenly dispersed and fully reacted to obtain nano-oxidized The cellulose slurry is the parent starch adhesive.

Sand the surface of the veneer with a moisture content of about 4.5% and a format of 300mm×300mm; apply the starch adhesive with the nano-oxidized cellulose slurry prepared in this example as the matrix evenly on the veneer with a sizing amount of 300g/ ^m2 Surface; then pre-press for 2 minutes under the pre-pressing machine; then perform hot-pressing under the conditions of hot-pressing 3MPa and hot-pressing time 1mm/min.

According to GB/T9846-2004 II class plywood standard, measure the plywood water resistance of the above-mentioned preparation; According to GB/T9846-2004 II class plywood standard, adopt tensile machine to measure (with reference to GB/T17657-1999 standard sample preparation) the bonding strength of plywood, the result As shown in Table 1.

Example 4:

A starch adhesive based on nano-oxidized cellulose slurry of the present invention, comprising the raw materials of the following components: 100 grams of oxidized cellulose slurry with an oxidation rate of 30% (solid content 12%), 40 grams of starch, 5 The gram mass concentration is 30% oxidant H ₂ O ₂ , 2 grams of stabilizer polyvinyl alcohol, 2 grams of antiseptic ammonium pentaborate and 2 grams of emulsified paraffin; the nanofiber length in the nano-oxidized cellulose is 1-100nm and the content is 70 %; the content of nanofibers with a length of 100-1000nm is 20%; the content of fibers with a length of 1 μm-10mm is 10%.

The preparation method of the starch adhesive based on the nano-oxidized cellulose slurry of the present embodiment comprises the following steps:

(1) Take 12 grams of pulp board, add 100 grams of concentration into a 60% sulfuric acid solution, shear and stir for 3 hours at a temperature of 55°C (shear rate is 5000rpm), then add 2 grams of oxidant with a mass concentration of 30% H ₂ O ₂ continued to shear and stir the reaction for 1.0h; finally, 800 grams of water was added to terminate the reaction, the obtained product was put into a dialysis bag, and dialyzed to pH = 1, the solid content was 12%, and the oxidation rate was 30%. Cellulose slurry; the nanofiber length distribution in the nano-oxidized cellulose slurry: 1-100nm, 70%; 100-1000nm, 20%; 1 μm-10mm, 10%.

(2) Take 100 grams of nano-oxidized cellulose slurry obtained in step (1), add 40 grams of starch and 5 grams of oxidant H ₂ O ₂ with a mass concentration of 30% in batches, add 4 grams of starch and 0.5 gram of oxidant for the first time Mass, fully stirred at 70°C for gelatinization reaction for 1h; for the second time, 16g of starch and 2.5g of oxidant, fully stirred at 70°C for 1h; for the third time, 20g of starch and 2g of oxidant were added, and fully stirred at 70°C 1h; then add 2 grams of stabilizer polyvinyl alcohol, 2 grams of preservative ammonium pentaborate, and 2 grams of emulsified paraffin, and stir well at 60°C until the components are evenly dispersed and fully reacted to obtain a nano-oxidized cellulose slurry. Parent starch adhesive.

Sand the surface of the veneer with a moisture content of about 4.5% and a format of 300mm×300mm; apply the starch adhesive with the nano-oxidized cellulose slurry prepared in this example as the matrix evenly on the veneer with a sizing amount of 300g/ ^m2 Surface; then pre-press for 2 minutes under the pre-pressing machine; then perform hot-pressing under the conditions of hot-pressing 3MPa and hot-pressing time 1mm/min.

According to GB/T9846-2004 II class plywood standard, measure the plywood water resistance of the above-mentioned preparation; According to GB/T9846-2004 II class plywood standard, adopt tensile machine to measure (with reference to GB/T17657-1999 standard sample preparation) the bonding strength of plywood, the result As shown in Table 1.

Comparative example:

The starch adhesive of this comparative example comprises the raw material of following components: 100 grams of distilled water, 30 grams of starch, 10 grams of dry nanocellulose, 1 gram of stabilizer polyvinyl alcohol, 1 gram of antiseptic ammonium pentaborate and 1 gram emulsified paraffin.

The preparation steps are as follows: add 30 grams of starch to 100 grams of distilled water at one time, fully stir at 60 ° C for 0.5 h, then add 10 g of dry nanocellulose, 1 gram of stabilizer polyvinyl alcohol, 1 gram of preservative ammonium pentaborate and 1 gram of emulsified paraffin, fully stirred at 50°C until the components are evenly dispersed, and then the starch adhesive is obtained.

Sand the surface of the veneer with a moisture content of about 4.5% and a format of 300mm×300mm; apply the ordinary starch adhesive prepared in this comparative example evenly on the surface of the veneer according to the sizing amount of 300g/m2 ^; Pre-press for 2 minutes; then perform hot-pressing under the conditions of hot-pressing 3MPa and hot-pressing time 1mm/min.

According to GB/T9846-2004 II class plywood standard, measure the plywood water resistance of the above-mentioned preparation; According to GB/T9846-2004 II class plywood standard, adopt tensile machine to measure (with reference to GB/T17657-1999 standard sample preparation) the bonding strength of plywood, the result As shown in Table 1.

Table 1 The strength and water resistance test results of starch adhesives:

Example 1 Example 2 Example 3 Example 4 Comparative Experiment Dry strength/MPa 1.85 1.90 2.62 2.32 1.01 Wet strength/MPa 0.64 0.71 0.91 0.78 0.26

It can be seen from Table 1 that the strength and water resistance of the starch adhesive using nano-oxidized cellulose slurry as the matrix of the present invention are significantly better than those of the ordinary adhesive in the comparative experiment.

Claims (8)

1. A kind of 1. starch adhesive using nano oxidized cellulose slurries as parent, it is characterised in that in parts by weight, including with The raw material of lower component：100 parts of oxygenation efficiency are 5%~30% nano oxidized cellulose slurries, 10~40 parts of starch, 2~5 parts of oxidations Agent, 0.1~2 part of stabilizer, 0.1~2 portion of preservative and 0.1~2 part of emulsified wax；In the nano oxidized cellulose slurries The oxycellulose mass fraction that fibre length is 1~100nm is 35%~70%；Fibre length is 100~1000nm oxygen Cellulose mass fraction is 20%~50%；The oxycellulose mass fraction that fibre length is 1 μm~10mm is 10%~ 15%.
2. 2. starch adhesive as claimed in claim 1, it is characterised in that the solid content of the nano oxidized cellulose slurries is 8%~12%.
3. 3. starch adhesive as claimed in claim 1, it is characterised in that the oxidant is H₂O₂Or/and NaClO；It is described steady It is macrogol to determine agent；The preservative is ammonium pentaborate.
4. A kind of 4. preparation method using nano oxidized cellulose slurries as the starch adhesive of parent, it is characterised in that including with Lower step：

   (1) 8~12 parts of pulp boards are taken, are added in 80~100 parts of sulfuric acid solutions, at a temperature of 50~55 DEG C shear agitation 1~ After 3h, add 1~2 part of oxidant and continue 0.5~1.0h of shear agitation reaction；200~1000 parts of water are eventually adding to terminate instead Should, product will be obtained and dialysed to pH=1~5, the nano oxidized cellulose slurries that oxygenation efficiency is 5%~30%；

   (2) 100 parts of nano oxidized cellulose slurries for taking step (1) to obtain, 10~40 parts of starch and 2~5 parts are added in batches Oxidant, 0.1~2 part of stabilizer, 0.1~2 portion of preservative and 0.1~2 part of emulsified wax are added after being sufficiently stirred, 50 Each component is stirred well at~70 DEG C to be uniformly dispersed, that is, obtains the starch adhesive.
5. 5. preparation method as claimed in claim 4, it is characterised in that in the step (2), add starch and oxidation in batches Agent concretely comprises the following steps：10%~15% of 5%~10% and oxidant quality of starch quality in proportioning is added for the first time, 0.5~1h of gelatinization reaction is sufficiently stirred at 50~70 DEG C；Second of 30~40% and the oxidant for adding starch quality in proportioning The 40%~50% of quality, 0.5~1h is sufficiently stirred at 50~70 DEG C；Third time add proportioning in starch quality 50%~ 65% and the 35%~50% of oxidant quality, it is sufficiently stirred 0.5~1h at 50~70 DEG C.
6. 6. preparation method as claimed in claim 4, it is characterised in that the nano oxidized cellulose slurry that the step (1) obtains The solid content of liquid is 8%~12%；Fibre length is 1~100nm oxycellulose in the nano oxidized cellulose slurries Mass fraction is 35%~70%；The oxycellulose mass fraction that fibre length is 100~1000nm is 20%~50%；It is fine It is 10%~15% to tie up the oxycellulose mass fraction that length is 1 μm~10mm.
7. 7. preparation method as claimed in claim 4, it is characterised in that the oxidant is H₂O₂Or/and NaClO；The stabilization Agent is macrogol；The preservative is ammonium pentaborate.
8. 8. preparation method as claimed in claim 4, it is characterised in that in the step (1), the mass concentration of sulfuric acid solution is 20%~60%；Shear rate is 2000~5000rpm.