CN108727893A - A method of preparing levelling agent using vinifera residue - Google Patents

Abstract

The present invention relates to a kind of methods preparing levelling agent using vinifera residue, including cellulose extraction and esterification technique in vinifera residue.By the traditional waste grape residue during Wine-making by extracting cellulose after removing the impurity such as lipophilic molecule, lignin, hemicellulose, carries out esterification using the cellulose of lower molecular weight after grape brewing fermentation and prepare high-quality levelling agent.Prepared cellulose ester-based levelling agent has important application power, levelling higher ranked in fields such as car paint, plastic paint, glass coatings.

Description

A method of preparing levelling agent using vinifera residue

Technical field

The present invention relates to a kind of levelling agent method, including cellulose extraction, cellulose esters are prepared using vinifera residue The method of change and levelling agent performance characterization, belongs to coating and levelling agent field.

Background technology

Coating is the organic matter of a kind of flow regime or pulverulence, can uniform fold on a surface of an, and securely Ground is attached to body surface.Coating can not only play protection, decoration function, but also have insulation, conduction, antistatic, temperature indicating, prevent The development of the specific functions such as mould, sterilization, coating technology reflects a national industrialization degree, the development of science and technology, Ren Minsheng Running water is put down and the composite factors such as defense force, it is just playing effect more and more outstanding in the national economic development.But it applies No matter which kind of application means material takes, after construction, there is the film forming procedure of evaporation of the solvent, polymer flow, due to solvent The wetness degree difference of evaporation, polymer and base material often results in paint film and tension gradient occurs, wrinkle occurs so as to cause paint film And shrinkage cavity, once there is this phenomenon, then the dicoration of paint film and the water resistance of paint film, solvent resistance can decline.

Levelling agent is a kind of common coating additive, it can promote coating formed during drying and forming-film one it is smooth, Smooth, uniform film.The design of levelling agent at present, which should ensure that, has the function of following three：（1）It reduces between coating and base material Surface tension, make coating and base material that there is best wetability, that is, reduce the tension gradient caused by solvent volatilizees, to mix Property restricted long-chain resin be main constituent, there are commonly polyacrylic acid lipid, cellaburate classes；（2）It can adjust molten The evaporation rate of agent, the mobility for reducing viscosity, improving coating, often with aromatic hydrocarbons, ketone, esters or more officials in solvent based coating Fine solvent-high boiling solvent the mixture that can be rolled into a ball is main composition, it has adjusted the evaporation rate of solvent, makes coating dry There is average evaporation rate and dissolving power during dry；（3）Monolayer can be formed in coating surface, to provide uniform table Face tension is mainly to form with the restricted long-chain silicon material fat of compatibility, and there are commonly diphenylpolysiloxane, aminomethyl phenyl is poly- Siloxanes, Organo-modified siloxanes, fluorinated siloxane etc..In addition fluorine-containing surfactant is for the resin of broad spectrum and molten Agent has excellent compatibility and surface-active, can effectively improve wellability, dispersibility, levelability.It is water-soluble in heat curing type There is good application in property epoxy, amino resins white coating materials.

Grape wine is a kind of fruit wine made as raw material using grape.Its alcoholic strength is less than white wine higher than beer.Nutrition is rich Richness, health-care effect are apparent.It can adjust the performance of metabolism, promote blood circulation, prevent cholesterol from increasing.Also there is profit The effect of urinating, exciting liver function and prevent aging.It is also to cure cardiopathic adjuvant, scurvy, anaemia, tinea pedis can be prevented The diseases such as disease, indigestion and eye keratitis.With the progress of social standard of living, the yield of grape wine increases year by year.In Portugal In the brewing process of grape wine, there are 20%~30% grape residual product, including the broken carpopodium generated of destemming, the skin after squeezing Slag, and turn tank, the wine mud precipitation etc. that traditional aging process generates.From the aspect of biological and chemical oxygen demand, because it is rich in organic Object seriously pollutes environment, and results in waste of resources.Therefore, the research of grape and by-product in wine industry is actively developed, It makes a silk purse out of a sow's ear, there is certain important economy and social effect.It includes extraction dietary fiber, color that traditional grape residue, which utilizes, Element, colourless phenolic acid and be used as animal plant feedstuff.Main utilize of the by-product generated in wine production remains in thick add Work level, such as simply it is processed into fertilizer, feed.In order to break through current techniques bottleneck, the comprehensive utilization of fruits and vegetables residue and height are realized Added value converts, and is actively developing correlative study both at home and abroad.

It realizes that the recycling of vinifera residue recycles using chemical means, dirt of the fruits and vegetables residue to environment can be reduced Dye, extension industry chain improve resource utilization and income space, are had a very important significance to developing a circular economy.Fiber Element is cheap, nontoxic, biodegradable, applies and pushes away Chen Zhixin, and the cellulose resource in vinifera residue Recycling is our focus.Vinifera residue contains more regular, the lower cellulose of molecular weight through everfermentation, relatively suitable It closes and carries out chemical modification preparation high added value Related product.

Invention content

Patent of the present invention is designed to provide a kind of method preparing levelling agent using vinifera residue.

In order to achieve the above objectives, specific technical solution of the present invention is：

（1）Cellulose is extracted with vinifera residue, extraction process includes：By vinifera residue toluene, methanol mixing 5 ~ 10 hours removing lipophilic molecules are extracted in solvent solution, solid residue is distributed in deionized water after filtering drying, is adjusted Between pH value is 3.5 ~ 4.5, a certain amount of sodium chlorite being added, is reacted 1 ~ 3 hour under 60 ~ 80 degrees Celsius, ethyl alcohol cleans 3 times, By in solid particle dispersions to deionized water after filtering drying, in mass ratio：60 ~ 80 degrees Celsius of 3 ~ 10% sodium hydroxide solution Lower reaction 4 hours, filtering, deionized water, which is cleaned to neutrality, dries.Wherein：By volume, toluene：Methanol=1 ~ 3：1；By quality Than solid residue：Sodium chlorite=1：1~3；In mass ratio, solid particle：Sodium hydroxide=1 ~ 10：1；

（2）Cellulose esterification prepares cellulose ester-based levelling agent, and esterification includes：Cellulose：N-butyric acie, acetic anhydride are dense Sulfuric acid, wherein in mass ratio, cellulose：N-butyric acie：Acetic anhydride：The concentrated sulfuric acid=100 ~ 500 ﹕, 100 ~ 200 ﹕, 0 ~ 20 ﹕ 20 ~ 200；Reaction Temperature：60 ~ 80 degrees Celsius；Reaction time：1 ~ 3 hour；Cellulose ester-based levelling agent is obtained after washing is dry；

Wherein, the cellulose is：Step（1）The cellulose of middle vinifera residue extraction.

Above-mentioned reaction system, which provides, a kind of preparing levelling agent method using vinifera residue.Therefore, the present invention claims It protects simultaneously and synthesizes levelling agent using above-mentioned reaction system.

Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：

（1）After the present invention prepares vinifera residue that levelling agent utilizes by microbial fermentation, molecular weight is relatively low, Ke Yishi Existing higher degree of esterification；

（2）The present invention can solve wine brewing a large amount of residue waste material in the process using vinifera residue levelling agent is prepared Change recycling problem, realization is turned waste into wealth.

Specific implementation mode

With reference to exemplary embodiments, the invention will be further described, but the present invention is not limited to following implementation cases Example.The method is conventional method unless otherwise specified.The raw material unless otherwise instructed can be from open commercial sources And it obtains.Chemical reagent used：Vinifera residue Yantai Zhongyu Group Co. Ltd.；Toluene analyzes pure Chinese medicines group chemistry examination Agent Co., Ltd；Methanol analyzes pure Sinopharm Chemical Reagent Co., Ltd.；Sodium chlorite analyzes pure Chinese medicines group chemical reagent Co., Ltd；The pure Sinopharm Chemical Reagent Co., Ltd. of ethanol analysis；Sodium hydroxide, which analyzes pure Chinese medicines group chemical reagent, to be had Limit company；N-butyric acie analyzes pure Sinopharm Chemical Reagent Co., Ltd.；Acetic anhydride analyzes the pure limited public affairs of Chinese medicines group chemical reagent Department；The concentrated sulfuric acid analyzes pure Sinopharm Chemical Reagent Co., Ltd..

Embodiment one：Vinifera residue extracts cellulose

By 1000 grams of dry slags of vinifera residue in toluene：Methanol volume ratio 2：It extracts 6 hours and removes in 1 mixed solvent solution Lipophilic molecule, filtering drying obtain solid residue；It weighs 500 grams of solid residues to be distributed in deionized water, adjusting pH value is 4.0 or so, it is added under 500 grams of 70 degrees Celsius of sodium chlorites and reacts 1 hour, ethyl alcohol cleans 3 times, and filtering drying obtains solid Grain.It weighs in 200 grams of solid particle dispersions to deionized water, is added 400 milliliters, the sodium hydroxide solution 60 of mass ratio 5% is Celsius The lower reaction of degree 4 hours, filtering, deionized water cleans to neutrality drying and obtains cellulose.

Embodiment two：The esterification technique of cellulose

Take 100 grams of the cellulose that will be obtained in case study on implementation one, be added 100 grams of n-butyric acies, in 20 grams of acetic anhydrides, under mechanical agitation by It is added dropwise to 20 milliliters of the concentrated sulfuric acid；Reaction temperature：60 degrees Celsius；Reaction is added 500 milliliters deionized water washing after 1 hour is dry It is dry to obtain cellulose esters.

Embodiment three：The characterization of cellulose esters structural behaviour

10 milligrams of cellulose esters prepared by case study on implementation two is taken to be dissolved in 5 milliliters of tetrahydrofuran solution, it is poly- using ultra high efficiency Spectrum is looked in conjunction（APC）, polystyrene is standard specimen, its number-average molecular weight 2.2 ten thousand or so of survey, molecular weight distribution is 1.5 or so；It takes It is 1.8s/pa that 100 milligrams of cellulose esters prepared by case study on implementation two, which selects its viscosity of rotational rheometer,.Nucleus magnetic hydrogen spectrum shows Its acetyl content 10.1%, bytyry content is 48.6%, and hydroxy radical content is 2.9% or so.Differential scanning calorimetry（DSC）It surveys Its bright fusing point of taking temperature is 168.6 degrees Celsius, and glass transition temperature is 125.2 degrees Celsius.It is added as coating additive There is preferable levelling effect, no shrinkage cavity to occur in polyacrylate coating.

Claims (2)

1. a kind of method preparing levelling agent using vinifera residue, including following 2 steps, it is characterised in that：

（1）Vinifera residue extracts cellulose, and extraction process includes：Vinifera residue is molten in the mixing of toluene, methanol 5 ~ 10 hours removing lipophilic molecules are extracted in agent solution, solid residue is distributed in deionized water after filtering drying, adjusts pH Between value is 3.5 ~ 4.5, a certain amount of sodium chlorite is added, is reacted 1 ~ 3 hour under 60 ~ 80 degrees Celsius, ethyl alcohol cleans 3 times, mistake By in solid particle dispersions to deionized water after filter drying, in mass ratio：Under 3 ~ 10% 60 ~ 80 degrees Celsius of sodium hydroxide solution Reaction 4 hours, filtering, deionized water, which is cleaned to neutrality, dries；

Wherein：By volume, toluene：Methanol=1 ~ 3：1；In mass ratio, solid residue：Sodium chlorite=1：1~3；By quality Than solid particle：Sodium hydroxide=1 ~ 10：1；

（2）Cellulose esterification prepares cellulose ester-based levelling agent, and esterification includes：Cellulose：N-butyric acie, acetic anhydride are dense Sulfuric acid, wherein in mass ratio, cellulose：N-butyric acie：Acetic anhydride：The concentrated sulfuric acid=100 ~ 500 ﹕, 100 ~ 200 ﹕, 0 ~ 20 ﹕ 20 ~ 200；Reaction Temperature：60 ~ 80 degrees Celsius；Reaction time：1 ~ 3 hour；Cellulose ester-based levelling agent is obtained after washing is dry；

Wherein, the cellulose is：Step（1）The cellulose of middle vinifera residue extraction.

2. a kind of extracting the levelling prepared by esterification after cellulose by described in claim 1 by vinifera residue Agent.