CN106565907B - The preparation method of the enhanced biology base nano rubber latex of nano-cellulose - Google Patents
The preparation method of the enhanced biology base nano rubber latex of nano-cellulose Download PDFInfo
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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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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Abstract
The invention discloses the preparation methods of the enhanced biology base nano rubber latex of nano-cellulose, using starch, plant fiber cellulose fiber as raw material, prepare nanocrystalline starch and nano-cellulose by enzymatic hydrolysis, chemical oxidation pre-treatment and mechanical treatment respectively first；Then nanocrystalline starch, nano-cellulose are mixed with natural non-grain degradable starch, is made into uniform dispersion mixing liquid, carries out activation modification processing；Then initiator is added into mixed liquor, causes the emulsion polymerization of double bond class monomer, nano-cellulose, nanocrystalline starch and non-grain degradable starch graft copolymer, the i.e. enhanced biology base nano rubber latex of nano-cellulose is finally made.The nano-cellulose that contains in biology base nano rubber latex, nanocrystalline starch component play the role of significantly increasing to the cohesive force of latex, have many advantages, such as environmentally protective, safety and sustainability simultaneously, the fields such as papermaking, weaving, packaging, daily use chemicals, building materials can be widely used in.
Description
Technical field
The present invention relates to a kind of preparation methods of the enhanced biology base nano rubber latex of nano-cellulose, belong to Chemical Engineering Technology neck
Domain.
Background technique
Adhesive refers to sticking and the effects of cohesion, two or more product or material can be made to connect by interface
Natural or synthesis, the organic or inorganic substance being connected together, is referred to as adhesive, is called binder.According to
The source of adhesive can be divided into natural glue and synthetic adhesive, such as natural rubber, pitch, rosin, gelatin, fiber
Element, amylan etc. belong to natural glue, and the various adhesives for using polymerization artificial synthesized belong to synthetic adhesive
Scope.Wherein, most of the raw material that synthetic adhesive uses are fossil class resources.
Since the 21th century, because exploiting, use environmental pollution, greenhouse gas emission, resource caused by fossil class resource
The problems such as exhausted, increasingly highlights, and causes whole world national governments and the highest attention and demand of the people.Meanwhile with the amount of containing
Abundant, inexpensive, renewable, green, the environmental-friendly natural biomass resource in source partially or completely replaces fossil class resource,
Have become industry and scientific circles study jointly, the lasting hot spot developed and focus.In adhesive industry, although synthetic adhesive
Production and application still occupy most ratios, but with the continuous development of science and technology, novel, haveing excellent performance, ring
All kinds of natural glues of border close friend have been flourished.
Currently, although some biological (starch base) latex products occurred in the market are generally deposited environmentally friendly and cheap
The disadvantages of adhesion strength is low, not resistant to water, easy to aging rotten, stability is poor, it is limited to petroleum base synthetic adhesive
The promotion of substitution ratio.
Summary of the invention
The shortcomings that present invention is for current synthetic adhesive, common biological latex products and deficiency, provide a kind of Nanowire
The preparation method of the enhanced biology base nano rubber latex of dimension element.
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of the enhanced biology base nano rubber latex of nano-cellulose, comprising the following steps:
(1) using starch, plant fiber cellulose fiber as raw material, respectively by digesting, at chemical oxidation pre-treatment and machinery
Reason, prepares nanocrystalline starch and nano-cellulose；
(2) the nanocrystalline starch of step (1) preparation, nano-cellulose are mixed with natural non-grain degradable starch, is made into
Even dispersion then carries out activation modification processing；It is anti-that emulsion polymerization finally is carried out to activation modification treated dispersion again
It answers, nano-cellulose, nanocrystalline starch and non-grain degradable starch emulsion graft copolymer is finally made, is i.e. nano-cellulose enhances
Type biology base nano rubber latex.
Further, the preparation method of the enhanced biology base nano rubber latex of above-mentioned nano-cellulose, wherein the shallow lake
Powder is one of cornstarch, tapioca, potato starch, rice starch or a variety of.
Further, the preparation method of the enhanced biology base nano rubber latex of above-mentioned nano-cellulose, wherein the plant
Fibres cellulose fiber is one of lumber fibre, grass fiber, cotton fiber, flaxen fiber, pulp fibers or a variety of.
Further, the preparation method of the enhanced biology base nano rubber latex of above-mentioned nano-cellulose, wherein step (1)
Described in enzymolysis processing endoglucanase (EG), exoglucanase (CBH), fiber contained using complex cellulase
Plain disaccharidase (BG)；Enzymolysis processing technique are as follows: firstly, water is added in reactor tank；Then, it weighs starch and fibrous raw material is added
Into reactor tank, it is made into the mixed liquor of 1~10% concentration, moderate-speed mixer；Then, the composite fibre of 1.0~10.0FPU/g is added
Plain enzyme, be added buffer solution control mixed liquor reaction system pH value be 5.0 ± 0.2, control the temperature of reaction system be 40~
60 DEG C, the reaction time is 1~3h.Starch, plant fiber cellulose fiber absolute dry mass ratio be (1~30): 1.
Further, the preparation method of the enhanced biology base nano rubber latex of above-mentioned nano-cellulose, it is characterised in that: step
Suddenly chemical oxidation pre-treatment described in (1) is the additionization in starch, plant cellulose fiber enzymatic hydrolysis treated reaction system
Learn oxidising agent, make oxidation after starch and plant fiber cellulose fiber mixed liquor carboxyl-content be at least up to 0.80mmol/g and
More than.
Further, chemical oxidation treatment described in step (1), wherein the chemical oxidation reagent is 2,2,6,6-
Tetramethyl piperidine nitrogen oxides, sodium bromide, sodium metaperiodate, sodium hypochlorite, sodium chlorite or hydrogen peroxide.
Further, mechanical treatment described in step (1), be using high pressure homogenizer, grinding and crushing machine, sand mill,
One of ball mill, ultrasonic cell disruptor are a variety of, to respectively by enzymatic hydrolysis and chemical oxidation treatment starch and
Plant fiber cellulose fiber mixed liquor applies mechanism, obtains the nanocrystalline starch with nano-scale and nano-cellulose；Its
In, the partial size of nanocrystalline starch is less than 100nm, and the fibril width of nano-cellulose is less than 100nm.
Further, in step (2), the over dry of starch and plant fiber cellulose fiber mixed liquor and natural non-grain degradable starch
Mass ratio is (1~10): 100.
Further, the processing of activation modification described in step (2) is one of etherificate, esterification, crosslinking or a variety of
Chemical modification processing.
Further, emulsion polymerization described in step (2) is added into activation modification treated dispersion
Initiator causes the emulsion polymerization of double bond class monomer.
Further, the performance indicator that the enhanced biology base nano rubber latex of nano-cellulose described in step (2) has
Are as follows: 50~100nm of partial size；Solid content 50 ± 2%；Viscosity≤500mPas；PH value 6.0-8.0；Mechanical stability (mass fraction)
≤ 0.03%；Coagulum content (mass fraction) (325 mesh)≤0.03%；40~55mN/m of surface tension；Glass transition temperature
(Tg) 10~50 DEG C.
The present invention has significant advantages and beneficial effects compared with prior art, embodies in the following areas:
1. the present invention has two kinds the biomass nano material of unique enhancement effect: nano-cellulose and nanocrystalline starch
Together with non-grain degradable starch, in such a way that emulsion graft copolymerization closes, being made has excellent high bonding force characteristic, nanoscale
The adhesive product of size has many advantages, such as that high cohesive force, good film-forming property, water resistant are grease proofing, adaptable, low in cost；
2. synthetic adhesive-carboxylic of the enhanced alternative Paper Coating of biology base nano rubber latex of nano-cellulose obtained
Base styrene-butadiene latex (SBR), substitution ratio reach 60% or more, and the IGT picking speed of coating paper (reflects the viscous of adhesive
Tie power) it is greater than 2.0m/s, it is able to satisfy the application requirement of Paper Coating High-performance adhesive completely；
3. biomass resource (plant fiber, starch of the raw material from recyclable regenerative, the nature amount of containing very abundant
Deng), biomass content is up to 90%, and it is degradable, it is environmentally protective, safe and efficient；Being produced into for end product can not only be reduced
This, improves performance, improves the competitiveness of product, promote greenization, the environmental protection of product, can also reduce to non-renewable change
The use of stone resource, reduce environmental pollution load and carbon emission, to industrial structure optimization, transition and upgrade, the sustainable health of society
Development all has a very important significance.
Specific embodiment
The present invention prepares the enhanced biology of nano-cellulose using nanotechnology, zymolysis technique, emulsion polymerization technology research and development
Base nano rubber latex belongs to novel biomass nano material, can be attributed to natural glue scope.It is that there is unique increase by two kinds
The potent biomass nano material answered: nano-cellulose and nanocrystalline starch pass through emulsion graft polymerization together with non-grain degradable starch
The mode of combined polymerization, it is obtained a kind of with excellent high bonding force characteristic, nano-grade size adhesive product, have high viscous
The advantages that tying power, good film-forming property, water resistant grease proofing, adaptable, low in cost.It is mainly used in papermaking, weaving, printing and packet
The fields such as dress, daily use chemicals, building materials, medicine, electronic product, performance bonding, bonding, rheological characteristic improvement, mechanical the effects of enhancing.Positioning
It is substituted in unsustainable, petroleum base synthetic adhesive large scale.
Embodiment 1:
Nanocrystalline starch and nano-cellulose are prepared first: the water of 2000g being added in the three-necked flask of 5000ml, are added
The broad-leaved wood fiber slurry that 40g original cornstarch, 20g have been crushed, is made into the dispersion that concentration is about 3%, and moderate-speed mixer is added
The pH value that buffer solution controls dispersion is 5.0 ± 0.2, and the complex cellulase of 2.0FPU/g, heating water bath, reaction is added
Temperature 60 C, reaction time 2.5h.Then TEMPO (2,2,6,6- tetramethyl piperidine oxidation is sequentially added into the dispersion
Object) 2.5g, sodium bromide 8.0g, liquor natrii hypochloritis 150g with the sodium hydroxide solution of 10% concentration control the oxidation reaction body
The pH value of system be 10.5,23 DEG C of reaction temperature, reaction time 1.5h.The carboxyl-content of starch and cellulose mixed liquor after oxidation
Reach 1.12mmol/g.Then mixed liquor is concentrated into 2.5% concentration, homogeneous is carried out to the concentration slurry with high pressure homogenizer
Change processing, pressure 80MPa recycle homogeneous 3 times, and the material of collection is nano-cellulose and nanocrystalline starch mixes
Body.
The preparation of the enhanced biology base nano rubber latex of nano-cellulose: in 200ml aqueous solution, non-grain degradable starch is added
100g, the homogeneous mixture 10g, NaH of the nano-cellulose of above-mentioned preparation and nanocrystalline starch2PO47g, moderate-speed mixer, in 60
2h is reacted under DEG C water bath with thermostatic control, activation modification processing is completed；It is added 5.0g emulsifier SDBS (neopelex), heating
To 85 DEG C, 0.3g ammonium persulfate is then added into the mixed liquor and is used as initiator, the acrylic acid of dropwise addition 6.8g is added after 10min
Hydroxyl ethyl ester, while 0.5g ammonium persulfate aqueous solution is added dropwise, 1h is added dropwise to complete, and is finally cooled to 40 after 85 DEG C of insulation reaction 1h
DEG C, adjusting pH value with ammonium hydroxide is 6.5, is discharged after stirring 30min to get the enhanced biology base nano rubber latex of nano-cellulose is arrived.
Embodiment 2:
Nanocrystalline starch and nano-cellulose are prepared first: the water of 2000g being added in the three-necked flask of 5000ml, are added
The cotton fiber slurry that 40g original cornstarch, 20g have been crushed, is made into the dispersion that concentration is about 2%, and buffering is added in moderate-speed mixer
The pH value that solution controls dispersion is 5.0 ± 0.2, and the complex cellulase of 3.5FPU/g, heating water bath, reaction temperature is added
60 DEG C, reaction time 3.5h.Then sodium metaperiodate 12.5g, sodium bicarbonate 5.0g are added into the dispersion, with 2% concentration
Sodium hydroxide solution, control the oxidation reaction system pH value be 8.5,45 DEG C of reaction temperature, reaction time 2.5h.After oxidation
Starch and the carboxyl-content of cellulose mixed liquor reach 1.35mmol/g.Then mixed liquor is concentrated into 2.5% concentration, used
High pressure homogenizer carries out homogenize process to the concentration slurry, and pressure 80MPa is recycled homogeneous 3 times, and the material of collection is nanometer
The homogeneous mixture of cellulose and nanocrystalline starch.
The preparation of the enhanced biology base nano rubber latex of nano-cellulose: in 200ml aqueous solution, non-grain degradable starch is added
100g, the homogeneous mixture 10g, NaH of the nano-cellulose of above-mentioned preparation and nanocrystalline starch2PO4 7g, moderate-speed mixer, in 60
2h is reacted under DEG C water bath with thermostatic control, activation modification processing is completed；It is added 5.0g emulsifier SDBS (neopelex), heating
To 85 DEG C, 0.3g ammonium persulfate is then added into the mixed liquor and is used as initiator, the acrylic acid of dropwise addition 6.8g is added after 10min
Hydroxyl ethyl ester, while 0.5g ammonium persulfate aqueous solution is added dropwise, 1h is added dropwise to complete, and is finally cooled to 40 after 85 DEG C of insulation reaction 1h
DEG C, adjusting pH value with ammonium hydroxide is 6.5, is discharged after stirring 30min to get the enhanced biology base nano rubber latex of nano-cellulose is arrived.
Embodiment 3:
Nanocrystalline starch and nano-cellulose are prepared first: the water of 2000g being added in the three-necked flask of 5000ml, are added
The cotton fiber slurry that 40g original cornstarch, 20g have been crushed, is made into the dispersion that concentration is about 2%, and buffering is added in moderate-speed mixer
The pH value that solution controls dispersion is 5.0 ± 0.2, and the complex cellulase of 3.5FPU/g, heating water bath, reaction temperature is added
60 DEG C, reaction time 3.5h.Then sodium metaperiodate 12.5g, sodium bicarbonate 5.0g are added into the dispersion, with 2% concentration
Sodium hydroxide solution, control the oxidation reaction system pH value be 8.5,45 DEG C of reaction temperature, reaction time 2.5h.After oxidation
Starch and the carboxyl-content of cellulose mixed liquor reach 1.35mmol/g.Then mixed liquor is concentrated into 2.5% concentration, used
High pressure homogenizer carries out homogenize process to the concentration slurry, and pressure 80MPa is recycled homogeneous 3 times, and the material of collection is nanometer
The homogeneous mixture of cellulose and nanocrystalline starch.
The preparation of the enhanced biology base nano rubber latex of nano-cellulose: in 200ml aqueous solution, non-grain degradable starch is added
100g, the homogeneous mixture 10g of the nano-cellulose of above-mentioned preparation and nanocrystalline starch, aluminate coupling agent 3.2g, in 40 DEG C
2h is reacted under water bath with thermostatic control, activation modification processing is completed；It is added 5.0g emulsifier SDBS (neopelex), is warming up to
85 DEG C, 0.3g ammonium persulfate is then added into the mixed liquor and is used as initiator, the metering system of dropwise addition 4.5g is added after 10min
Allyl propionate, while 1.3g ammonium persulfate aqueous solution is added dropwise, 1h is added dropwise to complete, and is finally cooled to 40 after 80 DEG C of insulation reaction 1h
DEG C, adjusting pH value with ammonium hydroxide is 6.5, is discharged after stirring 30min to get the enhanced biology base nano rubber latex of nano-cellulose is arrived.
The performance indicator of the above-mentioned enhanced biology base nano rubber latex of nano-cellulose are as follows: 50~100nm of partial size；Solid content 50
± 2%；Viscosity≤500mPas；PH value 6.0-8.0；Mechanical stability (mass fraction)≤0.03%；Coagulum content (quality
Score) (325 mesh)≤0.03%；40~55mN/m of surface tension；10~50 DEG C of glass transition temperature (Tg).
In conclusion the enhanced biology base nano rubber latex of nano-cellulose produced by the present invention, has cohesive force strong, biological
Matter content is high, being compatible with the environment property is good, pollution-free, the advantages that having a wide range of application.The synthetic adhesive-of alternative Paper Coating
Carboxylic styrene butadiene latex (SBR), substitution ratio reach 60% or more, and the IGT picking speed of coating paper (reflects adhesive
Cohesive force) it is greater than 2.0m/s, it is able to satisfy the application requirement of Paper Coating High-performance adhesive completely.
The raw material of the enhanced biology base nano rubber latex of nano-cellulose come from recyclable regenerative, the nature amount of containing very
Biomass resource (plant fiber, starch etc.) abundant, biomass content are up to 90%, degradable, environmentally protective, safety, height
Effect.Using this novel, high performance natural glue product, the production cost of end product can be not only reduced, is improved
Performance improves the competitiveness of product, promotes greenization, the environmental protection of product, can also reduce to non-renewable fossil resource
Use, reduce the pollutional load and carbon emission of environment, can to China's industrial structure optimization at this stage, transition and upgrade, society
Sustainable and healthy development all has a very important significance.
It should be understood that the foregoing is merely the preferred embodiment of the present invention, the power that is not intended to limit the invention
Sharp range；The description above simultaneously, should can be illustrated and implement for the special personage of correlative technology field, thus it is other without departing from
The equivalent change or modification completed under disclosed spirit, should be included in claim.
Claims (5)
1. the preparation method of the enhanced biology base nano rubber latex of nano-cellulose, it is characterised in that: the following steps are included:
(1) using starch, plant fiber cellulose fiber as raw material, pass through enzymatic hydrolysis, chemical oxidation pre-treatment and mechanical treatment, system respectively
It is standby to obtain nanocrystalline starch and nano-cellulose；
The enzymolysis processing contains endoglucanase (EG), exoglucanase (CBH), fibre using complex cellulase
Tie up plain disaccharidase (BG)；Enzymolysis processing technique are as follows: firstly, water is added in reactor tank；Then, it weighs starch and fibrous raw material adds
Enter into reactor tank, be made into the mixed liquor of 1~10% concentration, stirs；Then, the compound cellulose of 1.0~10.0FPU/g is added
Enzyme, the pH value that buffer solution control mixed liquor reaction system is added is 5.0 ± 0.2, and control temperature of reaction system is 40~60 DEG C,
Reaction time is 1~3h；Starch, plant fiber cellulose fiber absolute dry mass ratio be (1~30): 1；
The mechanical treatment is using in high pressure homogenizer, grinding and crushing machine, sand mill, ball mill, ultrasonic cell disruptor
It is one or more, to respectively by enzymatic hydrolysis and chemical oxidation treatment starch and plant fiber cellulose fiber mixed liquor apply machine
Tool effect, obtains the nanocrystalline starch with nano-scale and nano-cellulose；Wherein, the partial size of nanocrystalline starch is less than
The fibril width of 100nm, nano-cellulose are less than 100nm；
(2) the nanocrystalline starch of step (1) preparation, nano-cellulose are mixed with natural non-grain degradable starch, is made into uniform
Dispersion then carries out activation modification processing；Emulsion polymerization finally is carried out to activation modification treated dispersion again, most
Obtained nano-cellulose, nanocrystalline starch and non-grain degradable starch emulsion graft copolymer eventually, the i.e. enhanced life of nano-cellulose
Object base nano rubber latex；
The activation modification processing is one of etherificate, esterification, crosslinking or a variety of chemical modification processing；
The emulsion polymerization is that initiator is added into activation modification treated dispersion, causes double bond class monomer
Emulsion polymerization.
2. the preparation method of the enhanced biology base nano rubber latex of nano-cellulose according to claim 1, it is characterised in that:
The starch is one of cornstarch, tapioca, potato starch, rice starch or a variety of.
3. the preparation method of the enhanced biology base nano rubber latex of nano-cellulose according to claim 1, it is characterised in that:
The plant fiber cellulose fiber is one of lumber fibre, grass fiber, cotton fiber, flaxen fiber, pulp fibers or a variety of.
4. the preparation method of the enhanced biology base nano rubber latex of nano-cellulose according to claim 1, it is characterised in that:
Chemical oxidation pre-treatment described in step (1) is added in starch, plant cellulose fiber enzymatic hydrolysis treated reaction system
The carboxyl-content of chemical oxidation reagent, starch and plant fiber cellulose fiber mixed liquor after making oxidation is at least up to 0.80mmol/g
More than.
5. the preparation method of the enhanced biology base nano rubber latex of nano-cellulose according to claim 4, it is characterised in that:
The chemical oxidation reagent is 2,2,6,6- tetramethyl piperidine nitrogen oxides, sodium metaperiodate, sodium hypochlorite, sodium chlorite or peroxide
Change hydrogen.
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| CN106988137A (en) * | 2017-04-25 | 2017-07-28 | 华南理工大学 | A kind of clean preparation method of higher concentration nano-cellulose fibril |
| CN108130802A (en) * | 2017-12-14 | 2018-06-08 | 九洲生物技术（苏州）有限公司 | For the package body of sausages food |
| CN108265564A (en) * | 2017-12-14 | 2018-07-10 | 九洲生物技术（苏州）有限公司 | Fruit freshness preserving nanometer paper and preparation method thereof |
| CN108425267B (en) * | 2018-03-12 | 2020-10-02 | 万邦特种材料股份有限公司 | Preparation method of food oilproof paper |
| CN109320617B (en) * | 2018-09-18 | 2021-01-29 | 青岛科技大学 | Bio-based nano material and preparation method thereof |
| CN112482083A (en) * | 2020-11-24 | 2021-03-12 | 中国制浆造纸研究院有限公司 | Starch-based compound capable of improving oil resistance of paper |
| CN115559147B (en) * | 2021-07-02 | 2024-01-16 | 中国制浆造纸研究院有限公司 | Method for improving nano cellulose nano-fibrillation efficiency |
| CN114940843B (en) * | 2022-05-31 | 2023-07-25 | 深圳市凌普鑫科技有限公司 | High-stability water-based ink with surfactant and preparation method thereof |
| CN114805689A (en) * | 2022-06-01 | 2022-07-29 | 浙江歌瑞新材料有限公司 | Preparation method of nano-cellulose reinforced polyvinylidene fluoride composite material |
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