CN107955363A - A kind of method of ZnO@NCC compound particles modification biological base water polyurethane lotion and products thereof - Google Patents

A kind of method of ZnO@NCC compound particles modification biological base water polyurethane lotion and products thereof Download PDF

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Publication number
CN107955363A
CN107955363A CN201711274832.2A CN201711274832A CN107955363A CN 107955363 A CN107955363 A CN 107955363A CN 201711274832 A CN201711274832 A CN 201711274832A CN 107955363 A CN107955363 A CN 107955363A
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ncc
zno
compound particles
base water
nano
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CN107955363B (en
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马建中
罗宗武
周建华
闫凯
张雷
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of method of ZnO@NCC nano-complex particles modification biological base water polyurethane lotion：Alkali source, amine, zinc source, nano-cellulose, water are uniformly mixed, form the alkaline solution of nano-cellulose；Hydro-thermal reaction is carried out in 80 ~ 160 DEG C, obtains nano-complex particle；Nano-complex particle is uniformly mixed with biological base water polyurethane.The invention also discloses the modified aqueous polyurethane prepared using this method, its quality formula includes：1 part of ZnO@NCC compound particles, 10 ~ 100 parts of aqueous polyurethane emulsion；ZnO@NCC compound particles are reacted to obtain by the mixture comprising following mass percent component：Alkali source 5 ~ 15%, amine 6 ~ 20%, zinc source 4 ~ 25%, water 35 ~ 84.9%, nano-cellulose 0.1 ~ 5%.Method of modifying of the present invention is simple, can improve ultraviolet-resistent property, mechanical performance etc..

Description

A kind of method of ZnO@NCC compound particles modification biological base water polyurethane lotion and Its product
Technical field
The present invention relates to polyurethane material technical field, more particularly to a kind of ZnO NCC compound particle modification biologicals Ji Shui Method of property polyaminoester emulsion and products thereof.
Background technology
With petering out for fossil resources, sight is gradually focused on the utilization of renewable resource by people.Guanidine glue is derived from The endosperm of cluster bean, contains great amount of hydroxy group on strand, can substitute part fossil resources polyalcohol.Aqueous polyurethane （WPU）It is the environment-friendly material using water as decentralized medium, has the characteristics that nontoxic and nonflammable, is widely used in skin The fields such as leather, coating, weaving.However, WPU in preparation process, introduces hydrophilic radical on strand, it is most of water-based in addition Polyurethane is all linear structure, so its glue film strength is relatively low.For WPU in application aspects such as leather finish, coating for wall surface, it is anti- UV resistance is relatively weak.Therefore aqueous polyurethane emulsion is badly in need of raising in terms of mechanical property and uvioresistant, if by guanidine glue It is incorporated into polyurethane backbone, prepares bio-based polyurethane lotion, then can improves its mechanical property.
Nano-cellulose (NCC), is to obtain a kind of cellulose of Nano grade through hydrolysis by natural plant fibre.Length exists 10-1000nm, diameter have the performance such as high-specific surface area, low-density and high-modulus, renewable, biodegradable in 5-20nm. Nano zine oxide (ZnO) particle size is 1 ~ 100nm, has good uv-shielding capacity.This research is using NCC as mould Plate, growth ZnO are prepared ZnO@NCC compound particles, its physical blending are incorporated into bio-based aqueous polyurethane emulsion.Can To assign the more preferable ultraviolet-resistent property of polyurethane, mechanical performance, further expand its application range.
The content of the invention
In order to overcome the above-mentioned deficiency of the prior art, it is an object of the invention to provide a kind of ZnO@NCC compound particles to change The method of property bio-based aqueous polyurethane emulsion.Obtained complex emulsions have excellent anti-ultraviolet property, mechanical performance etc..
To achieve these goals, the technical solution adopted in the present invention is a kind of ZnO@NCC compound particle modification biologicals The method of base water polyurethane lotion, specifically includes following steps：
Step 1：Alkali source, amine, zinc source, nano-cellulose, water are uniformly mixed, form the alkaline solution of nano-cellulose；
Step 2：Mixture in step 1 is fitted into hydrothermal reaction kettle, for a period of time, centrifuge washing obtains ZnO@to insulation reaction The compound particle of NCC.
Step 3：By the nano-complex particle for obtaining ZnO NCC in step 2 and biological base water polyurethane（The patent No.： CN201710373705.1）It is uniformly mixed, obtains stable ZnO@NCC compound particle modification biological base water polyurethane lotions.
The features of the present invention also resides in：
Step 1 is specifically implemented in accordance with the following methods：
By alkali source 5 ~ 15%, amine 6 ~ 20%, zinc source 4 ~ 25%, water 35 ~ 84.9%, nano-cellulose 0.1 ~ 5%, the above components matter The summation for measuring content is 100%.It is loaded into beaker, stirs evenly.
Alkali source is one kind or its mixture in sodium hydroxide, potassium hydroxide or barium hydroxide；
Zinc source is the mixture of zinc chloride, zinc nitrate, zinc acetate, one kind of zinc sulfate or its component；
Amine is ammonium hydroxide, hexamethylenetetramine or one kind of diethanol amine or the mixture of its component；
Step 2 is specifically implemented in accordance with the following methods：
The mixture that will be obtained through step 1, is fitted into hydrothermal reaction kettle, and 6 ~ 14h is reacted at 80 ~ 160 DEG C, and centrifuge washing obtains The compound particle of ZnO@NCC.
Step 3 is specifically implemented in accordance with the following methods：
Step 3.1：According to mass ratio 1:10 ~ 100 weigh the ZnO@NCC compound particles and bio-based water obtained through step 2 respectively Property polyaminoester emulsion：
Step 3.2：ZnO@NCC compound particles through step 3.1 and bio-based aqueous polyurethane emulsion are mixed into stirring 1h ~ 6h, obtains ZnO@NCC compound particle modification biological base water polyurethane lotions.
Beneficial effects of the present invention：
（1）The compound particle that the present invention selects is homemade ZnO@NCC compound particles modification biological base water polyurethane lotion Method, method of modifying are simple；
（2）A kind of method of ZnO@NCC compound particles modification biological base water polyurethane lotion of the present invention, by bio-based water Property polyurethane in add ZnO@NCC compound particles, ultraviolet-resistent property, mechanical performance of material etc. can be further improved.
Embodiment
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiments.
Embodiment 1
Take sodium hydroxide 5g as alkali source, take industrial ammonia 6g as amine, and weigh zinc acetate 5g, nano-cellulose 0.1g, Mixture gross mass 100g is added water to, 1h is stirred, is uniformly mixed, is received to raw material
Rice cellulose alkaline solution.Hydro-thermal reaction, 80 DEG C of reaction temperature, during reaction are carried out to foregoing nano-cellulose alkaline solution Between 14h, separation, washing, desciccate, obtain the compound particle of [email protected] to quality
It is 1 according to mass ratio:10 weigh ZnO@NCC compound particles and bio-based aqueous polyurethane emulsion respectively, by what is weighed ZnO@NCC compound particles and bio-based aqueous polyurethane emulsion are uniformly mixed stirring 1h, obtain ZnO@NCC compound particles and are modified life Thing base water polyurethane lotion.
Embodiment 2
Take barium hydroxide 5g to take urea 6g as amine as alkali source, and weigh zinc acetate 5g, nano-cellulose 0.15g, add water To mixture gross mass 100g, 2h is stirred, is uniformly mixed to raw material, obtains nano-cellulose alkaline solution.To foregoing Nanowire The plain alkaline solution of dimension carries out hydro-thermal reaction, and 100 DEG C, reaction time 12h of reaction temperature, separation, washing, desciccate, obtain The compound particle of [email protected] is 1 according to mass ratio:20 weigh ZnO NCC compound particles and biological base water polyurethane breast respectively Liquid, is uniformly mixed stirring 2h by the ZnO@NCC compound particles and bio-based aqueous polyurethane emulsion that weigh, obtains ZnO@NCC and answer Close particle modified bio-based aqueous polyurethane emulsion.
Embodiment 3
Sodium hydroxide 5g is taken to take urea 6g and hexamethylenetetramine 3g as amine, and weigh zinc nitrate 8g, nanometer as alkali source Cellulose 0.15g, adds water to mixture gross mass 100g, stirs 2h, is uniformly mixed to raw material, it is molten to obtain nano-cellulose alkalescence Liquid.To foregoing nano-cellulose alkaline solution carry out hydro-thermal reaction, 100 DEG C, reaction time 14h of reaction temperature, separation, washing, Desciccate, obtains the compound particle of [email protected] is 1 according to mass ratio:50 weigh ZnO@NCC compound particles and biology respectively Base water polyurethane lotion, stirring 2h is uniformly mixed by the ZnO@NCC compound particles and bio-based aqueous polyurethane emulsion that weigh, Obtain ZnO@NCC compound particle modification biological base water polyurethane lotions.
Embodiment 4
Sodium hydroxide 10g is taken to take urea 6g and hexamethylenetetramine 7g as amine, and weigh zinc chloride 15g, receive as alkali source Rice cellulose 2g, adds water to mixture gross mass 100g, stirs 2h, is uniformly mixed to raw material, it is molten to obtain nano-cellulose alkalescence Liquid.To foregoing nano-cellulose alkaline solution carry out hydro-thermal reaction, 120 DEG C, reaction time 10h of reaction temperature, separation, washing, Desciccate, obtains the compound particle of [email protected] is 1 according to mass ratio:60 weigh ZnO@NCC compound particles and biology respectively Base water polyurethane lotion, stirring 2h is uniformly mixed by the ZnO@NCC compound particles and bio-based aqueous polyurethane emulsion that weigh, Obtain ZnO@NCC compound particle modification biological base water polyurethane lotions.
Embodiment 5
Sodium hydroxide 15g is taken to take urea 6g and diethanol amine 14g as amine, and weigh zinc sulfate 25g, nanometer as alkali source Cellulose 5g, adds water to mixture gross mass 100g, stirs 2h, is uniformly mixed to raw material, obtains nano-cellulose alkaline solution. Hydro-thermal reaction, 160 DEG C, reaction time 7h of reaction temperature, separation, washing, drying are carried out to foregoing nano-cellulose alkaline solution Product, obtains the compound particle of [email protected] is 1 according to mass ratio:70 weigh ZnO@NCC compound particles and bio-based water respectively Property polyaminoester emulsion, by the ZnO@NCC compound particles and bio-based aqueous polyurethane emulsion that weigh be uniformly mixed stirring 2h, obtain ZnO@NCC compound particle modification biological base water polyurethane lotions.
Embodiment 6
Using unmodified bio-based aqueous polyurethane emulsion as blank sample, under the same testing conditions with the sample of embodiment 1 ~ 3 Product carry out the performances such as emulsion appearance, freeze-thaw stability, bin stability, film appearance, mechanical property, uvioresistant performance and are commented Valency, obtains 1 result of table.Table 1 is water-based poly- for the modified bio-based aqueous polyurethane emulsion of embodiment 1 ~ 3 and unmodified bio-based Urethane emulsion property test result.
1 data of table show that ZnO@NCC compound particle modification biological base water polyurethane lotions prepared by the present invention, are compared In the raising of blank emulsion mechanical property, uvioresistant performance.Wherein, the tensile strength of the sample of embodiment 2 is improved compared with blank sample 88.6%, the elongation at break of the sample of embodiment 2 reduces 44.2% compared with blank sample；Embodiment 1 ~ 3 shows ultraviolet Certain assimilation effect.The above results show that the present invention in aqueous polyurethane by adding the nano combined grains of ZnO@NCC Son, further improves the performances such as ultraviolet-resistent property and the mechanical performance of material.

Claims (10)

  1. A kind of 1. method of the lotion of ZnO@NCC nano-complex particle modification biological base water polyurethanes, it is characterised in that including Following steps：
    Step 1：Alkali source, amine, zinc source, nano-cellulose and water are uniformly mixed, form the alkaline solution of nano-cellulose；
    Step 2：Mixed liquor in step 1 is subjected to hydro-thermal reaction in 80 ~ 160 DEG C, after the reaction was complete, obtains receiving for ZnO@NCC Rice compound particle；
    Step 3：The nano-complex particle for obtaining ZnO@NCC in step 2 is uniformly mixed with bio-based aqueous polyurethane emulsion, Obtain stable ZnO@NCC nano-complex particle modification biological base water polyurethane lotions.
  2. 2. a kind of method of ZnO@NCC compound particles modification biological base water polyurethane lotion according to claim 1, its It is characterized in that, the alkali source includes sodium hydroxide, potassium hydroxide, barium hydroxide or its mixture.
  3. 3. a kind of method of ZnO@NCC compound particles modification biological base water polyurethane lotion according to claim 1, its It is characterized in that, the zinc source includes zinc chloride, zinc nitrate, zinc acetate, zinc sulfate or its mixture.
  4. 4. a kind of method of ZnO@NCC compound particles modification biological base water polyurethane lotion according to claim 1, its It is characterized in that, the amine includes ammonium hydroxide, hexamethylenetetramine, diethanol amine or its mixture.
  5. 5. a kind of method of ZnO@NCC compound particles modification biological base water polyurethane lotion according to claim 1, its It is characterized in that, the bio-based aqueous polyurethane emulsion is obtained according to the patent of Publication No. CN201710373705.1.
  6. 6. a kind of method of ZnO@NCC compound particles modification biological base water polyurethane lotion according to claim 1, its It is characterized in that, the step 2 specifically includes, and the mixed liquor that step 1 is obtained, is fitted into hydrothermal reaction kettle, anti-at 80 ~ 160 DEG C Answer 6 ~ 14h.
  7. 7. a kind of method of ZnO@NCC compound particles modification biological base water polyurethane lotion according to claim 1, its It is characterized in that, after the completion of the hydro-thermal reaction of the step 2, centrifuge washing, obtains the compound particle of ZnO@NCC.
  8. 8. a kind of method of ZnO@NCC compound particles modification biological base water polyurethane lotion according to claim 1, its It is characterized in that, the step 3 specifically includes：Bio-based aqueous polyurethane emulsion is weighed respectively and ZnO@NCC that step 2 obtains Compound particle, mixes stirring 1h ~ 6h by ZnO@NCC compound particles and bio-based aqueous polyurethane emulsion, obtains ZnO@ NCC compound particle modification biological base water polyurethane lotions.
  9. 9. the ZnO NCC compound particle modification biological base water polyurethanes prepared using any one of claim 1 ~ 8 the method.
  10. 10. a kind of ZnO@NCC compound particles modification biological base water polyurethane lotion according to claim 9, its feature It is, is made by the mixture of the component including following mass fraction：
    1 part of ZnO@NCC compound particles
    10 ~ 100 parts of bio-based aqueous polyurethane emulsion；
    Wherein, ZnO@NCC compound particles are made by the mixture of the component including following mass percent：
    Alkali source 5 ~ 15%
    Amine 6 ~ 20%
    Zinc source 4 ~ 25%
    Water 35 ~ 84.9%
    Nano-cellulose 0.1 ~ 5%.
CN201711274832.2A 2017-12-06 2017-12-06 Method for modifying bio-based aqueous polyurethane emulsion by ZnO/NCC nano composite particles and product thereof Active CN107955363B (en)

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CN110919804A (en) * 2019-11-07 2020-03-27 浙江省林业科学研究院 Bamboo wood enhanced synergistic treatment method

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CN108752564A (en) * 2018-05-04 2018-11-06 陕西科技大学 In-situ polymerization prepares the synthetic method of ZnO/ modifying nanometer cellulose aqueous polyurethanes
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