CN108949372A - A kind of fabric washing liquid of the enzyme preparation containing polymer overmold and preparation method thereof - Google Patents
A kind of fabric washing liquid of the enzyme preparation containing polymer overmold and preparation method thereof Download PDFInfo
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- CN108949372A CN108949372A CN201810857054.8A CN201810857054A CN108949372A CN 108949372 A CN108949372 A CN 108949372A CN 201810857054 A CN201810857054 A CN 201810857054A CN 108949372 A CN108949372 A CN 108949372A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38672—Granulated or coated enzymes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
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Abstract
The present invention relates to daily chemical product fields, disclose a kind of fabric washing liquid and preparation method thereof of enzyme preparation containing polymer overmold, the fabric washing includes: nonionic surfactant 15-35g, amphoteric surfactant 0-10g, polymer overmold enzyme preparation 0.5-5g, marine algae extract 0.1-3g, sodium citrate 0.1-5g, acid-base modifier 0-5g, washing assisant 0.1-10g, deionized water 40-80g.Contain polymer overmold enzyme preparation in cleaning solution of the present invention, under polymer overmold, enzyme preparation not vulnerable to the influence of other reagents in temperature, formula, inhibition, can remain higher enzymatic activity during storage.And at the same time the polymer overmold enzyme preparation is not easily settled in liquid detergent.
Description
Technical field
The present invention relates to the fabric washing liquid of daily chemical product field more particularly to a kind of enzyme preparation containing polymer overmold and its
Preparation method.
Background technique
Fabric washing liquid is also known as liquid detergent, working principle and traditional washing powder, and soap is similar, and effective component is all table
Face activating agent.Difference is: what traditional washing powder and soap generallyd use is anionic surfactant, is with alkyl sulphur
Based on sour sodium and odium stearate, alkaline stronger (pH is generally higher than 10 after the washing powder of standardized amount is dissolved in water), and then using
When it is larger to the stimulation of skin and injury.And liquid detergent mostly uses nonionic surface active agent, the pH of its own pH is generally
Alkalescent in 8-10 or so, and is added in water and is followed by weakly acidic pH (pH is 7-7.5 or so), more mild to skin, and arranges
It after entering nature, degrades faster compared with washing powder, therefore liquid detergent becomes the detergent of a new generation in recent years.
The effective component of liquid detergent is mainly nonionic surface active agent, and structure includes water-wet side and hydrophobic end,
Then middle hydrophobic end separates spot and fabric by physical motion (such as hand rubbing, machine movement) in conjunction with spot.Surface simultaneously
Activating agent reduces the tension of water, enables water to reach fabric surface, effective component is made to play a role.
In recent years, occur a large amount of liquid detergent containing enzyme in the market, be added to a variety of enzyme preparations, such as alkali in enzyme liquid detergent
Property protease preparation and alkaline fat enzyme preparation etc..These enzyme preparations not only can effectively remove the spot on clothing, but also
There is no toxic action to human body, and these enzyme preparations and its decomposition product can be decomposed by the microorganisms, and not polluted the environment.Institute
With enzyme liquid detergent receives the popular welcome of people.
But the enzymatic activity of enzyme preparation is limited by many factors, such as the inhibition of pH, temperature, other auxiliary agents etc..Especially
Ground, after liquid detergent is made, enzyme preparation is easy to be influenced by factors such as the inhibition of other reagents in storage temperature, liquid detergent, enzyme
Preparation is easy to inactivate in advance, not easy to maintain, further, since prolonged during storage stand, it is heavy that enzyme preparation is also easy to happen
Drop, the dispersibility in liquid detergent are poor.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of fabric washing liquid of enzyme preparation containing polymer overmold and
Preparation method.Contain polymer overmold enzyme preparation in cleaning solution of the present invention, under polymer overmold, enzyme preparation is in storage process
In not vulnerable to the influence of other reagents in temperature, formula, inhibit, can remain higher enzymatic activity.And at the same time this is poly-
It is not easily settled in liquid detergent to close object cladding enzyme preparation.
The specific technical proposal of the invention is: a kind of fabric washing liquid of enzyme preparation containing polymer overmold, including it is following heavy
Measure the component of part:
15-35 parts of nonionic surfactant,
0-10 parts of amphoteric surfactant,
0.5-5 parts of polymer overmold enzyme preparation,
0.1-3 parts of marine algae extract,
0.1-5 parts of sodium citrate,
0-5 parts of acid-base modifier,
0.1-10 parts of washing assisant,
40-80 parts of deionized water.
Contain polymer overmold enzyme preparation in cleaning solution of the present invention, under polymer overmold, enzyme preparation is protected, and is being stored up
During depositing higher enzymatic activity can not be remained vulnerable to the influence of other reagents in temperature, formula, inhibition.
Specifically, the polymer that the present invention is used to coat enzyme has specific pH sensibility, and pH susceptibility is the present invention
It is special that people is directed to cleaning solution system of the invention: when in the water that it is in pH=8-10 (cleaning solution itself pH), this is poly-
Adduct molecule chain both ends are collapsed, and so as to tightly wrap up enzyme, are played a protective role to enzyme, and the shadow of outer bound pair enzymatic activity is reduced
It rings, therefore enzyme not easy in inactivation when cleaning solution stores.And when it is in the water of pH=7-7.5 (added with the water of cleaning solution when laundry)
When middle, which, which can unfold, is stretched, and enzyme is released quickly against in water, it is made to play effect.
As described in the background art, since cleaning solution is stood for a long time during storage, enzyme preparation is easy to happen heavy
Drop causes the dispersibility in its cleaning solution poor.For this purpose, the present invention makes two o'clock improvement: 1, addition seaweed is extracted in formula
Object, marine algae extract is dissolved in after water can form a small amount of solid after adding proper content in viscous liquid in cleaning solution
Spacial framework, and enzyme preparation is locked in Mini-type Grid one by one, increases steric hindrance, it is made to be difficult to settle,
Accumulation.2, after the polymer of cladding enzyme is compounded with marine algae extract, its own can also be constituted with marine algae extract synergy
Three-dimensional net structure further increases steric hindrance.Further, since the polymer (pH=7-7.5) molecule when washing clothing
Chain, which is unfolded, to be stretched, and all groups exposure on strand, these groups, which can also play, prevents spot particle secondary deposition
Effect also has certain anti-deposit effect in the case where additionally not adding the auxiliary agents such as antiprecipitant, achieves many things at one stroke.
Preferably, the nonionic surfactant is selected from fatty alcohol polyoxyethylene ether, ethoxylated fatty acid
At least one of ester, alkanolamide and alkyl glycosides.
Preferably, the amphoteric surfactant is selected from cocamidopropyl betaine, dimethyl
At least one of base amine second lactone.
Preferably, the polymer overmold enzyme preparation is the complex enzyme by polymer overmold.
Preferably, the complex enzyme is in alkali protease, alkaline lipase, amylase and cellulase
At least two.
Preferably, the polymer overmold enzyme preparation the preparation method is as follows:
A 100 parts of caprolactones are mixed with 2-4 parts of benzyl alcohols, 1-2 parts of stannous octoates), react 8- at 120-130 DEG C
12h is dissolved reaction product with chloroform, and then absolute methanol solution precipitates, and obtains the modified polycaprolactone of terminal hydroxy group；Take 10 parts of ends
Hydroxyl modification polycaprolactone is dissolved in chloroform, sequentially adds 0.5-1 parts of 2- (dodecyl trithiocarbonic acid ester group) -2- methyl-prop
Acid, 0.5-1 parts of n-hydroxysuccinimide/dicyclohexylcarbodiimides, sufficiently after reaction, filtering, anhydrous methanol precipitation filtrates,
Obtain polycaprolactone initiator.
B it) takes 100 parts of lactides to mix with 1-2 parts of benzyl alcohols, 0.5-1 parts of stannous octoates, reacts 8- at 120-130 DEG C
12h is dissolved reaction product with chloroform, and then absolute methanol solution precipitates, and obtains terminal hydroxy group polydactyl acid.
C it) takes 1 part of polycaprolactone initiator to be dissolved in dimethyl sulfoxide, 0.01-0.05 parts of azodiisobutyronitriles is added, connect
1-3 parts of histidines of addition, polymerize 4-8h at 55-65 DEG C；0.5-1.5 parts of terminal hydroxy group polydactyl acids are added again, and heat preservation is poly-
6-10h is closed, with n-hexane to reaction liquid precipitate, obtains polymer.
D it) disperses 10 parts of polymer in deionized water, tune pH is 6-7.5, adds 5-15 parts of complex enzymes, agitating and heating
To 30-40 DEG C, ultrasonic disperse is uniform, after standing adsorption 2-6h, adjusts pH and is greater than 8, dialysis obtains polymer overmold enzyme preparation.
Above-mentioned substance number is parts by weight.
The molecular backbone of polymer of the invention has three block structure, respectively polycaprolactone, histidine and polylactic acid,
When being had characteristics that in the water for being in pH=8-10 (cleaning solution itself pH) when it by the polymer that above-mentioned three block is constituted,
The mid-block of the polymer is rendered as positively charged (isoelectric point of histidine is 7.6 or so), and its both ends block is presented
To be negatively charged, due to the principle that there is a natural attraction between the sexes, strand both ends phase mid-block is collapsed, so as to which enzyme is tightly wrapped up,
It plays a protective role to enzyme.And when in the water that it is in pH=7-7.5 (added with the water of cleaning solution when laundry), the polymer
Three sections of blocks on strand are rendered as positively charged, and due to the principle that identical charges repel each other, strand, which can unfold, to be stretched, by enzyme
It is released quickly against in water, it is made to play effect.The polymer is present invention cleaning solution system according to the present invention and is specifically designed
, it is not belonging to the prior art.
Further, it should be noted that since polymer of the invention can change structure under different pH environment, this
Invention, which is not added especially, to be had the anionic surfactant that centainly influences on it and is not added or less plus amphoteric surfactant,
But based on nonionic surfactant.
Preferably, the molecular weight of the polymer is 8-12w.
Preferably, the partial size of the polymer overmold enzyme preparation is 100-500nm.
The partial size of enzyme is in tens nanometer ranges, it is therefore desirable to by the molecular weight design of polymer in above-mentioned resonable degree, with
The cladding to enzyme can be better achieved.
Preferably, the washing assisant is in brightening agent, softening agent, essence, pigment, preservative and resist agent
At least one.
A kind of preparation method of the fabric washing liquid of the enzyme preparation containing polymer overmold, comprising the following steps:
1) nonionic surfactant, amphoteric surfactant, marine algae extract are added in deionized water according to the ratio,
It is stirred evenly at 30-40 DEG C, obtains viscous solution.
2) sodium citrate, washing assisant are added into viscous solution, are uniformly dispersed at 30-40 DEG C, then acid adding alkali tune
It saves agent and pH value of solution is adjusted to 8-10, then add polymer overmold enzyme preparation, used while adding polymer overmold enzyme preparation
Acid-base modifier maintains pH value of solution in 8-10；Fabric washing liquid is made after mixing evenly.
It is compared with the prior art, the beneficial effects of the present invention are:
Contain polymer overmold enzyme preparation in cleaning solution of the present invention, under polymer overmold, enzyme preparation is during storage
Not vulnerable to the influence of other reagents in temperature, formula, inhibit, can remain higher enzymatic activity.And at the same time the polymerization
It is not easily settled in liquid detergent that object coats enzyme preparation.
Specific embodiment
The present invention will be further described with reference to the examples below.
Embodiment 1
A kind of fabric washing liquid of the enzyme preparation containing polymer overmold, comprising:
Fatty alcohol polyoxyethylene ether 35g,
Polymer overmold enzyme preparation 3g,
Marine algae extract 1g,
Sodium citrate 1g,
Appropriate acid-base modifier,
Brightening agent 1g, essence 1g are restored,
Deionized water 55g.
A kind of preparation method of the fabric washing liquid of the enzyme preparation containing polymer overmold, comprising the following steps:
Polymer overmold enzyme preparation it is pre-prepared:
A 100g caprolactone is mixed with 3g benzyl alcohol, 1.5g stannous octoate), reacts 10h at 125 DEG C, it will be anti-with chloroform
Product is answered to dissolve, then absolute methanol solution precipitates, and obtains the modified polycaprolactone of terminal hydroxy group；The modification of 10g terminal hydroxy group is taken to gather in oneself
Ester is dissolved in chloroform, sequentially adds 0.8g 2- (dodecyl trithiocarbonic acid ester group) -2 Methylpropionic acid, 0.8gN- hydroxyl amber
Amber acid imide/dicyclohexylcarbodiimide, sufficiently after reaction, filtering, anhydrous methanol precipitation filtrates obtain polycaprolactone initiation
Agent.
B it) takes 100g lactide to mix with 1.5g benzyl alcohol, 0.8g stannous octoate, reacts 10h at 125 DEG C, it will with chloroform
Reaction product dissolution, then absolute methanol solution precipitates, and obtains terminal hydroxy group polydactyl acid.
C it) takes 1g polycaprolactone initiator to be dissolved in dimethyl sulfoxide, 0.01g azodiisobutyronitrile is added, then adds 2g
Histidine polymerize 6h at 60 DEG C；1g terminal hydroxy group polydactyl acid is added again, and heat preservation polymerization 8h sinks to reaction solution with n-hexane
It forms sediment, obtains polymer.
D it) disperses 10g polymer in deionized water, adjusting pH is 7, addition 10g complex enzyme (alkali protease, alkaline rouge
Fat enzyme), 35 DEG C are heated with stirring to, ultrasonic disperse is uniform, and after standing adsorption 4h, adjusting pH is 9, dialysis, and obtaining molecular weight is 8-
12w, the polymer overmold enzyme preparation that partial size is 100-500nm.
Restore the pre-prepared of brightening agent:
A) magnesium and zinc are dissolved in nitric acid solution respectively, the 10-20wt% magnesium nitrate solution containing hydrogen is made and contained
There is the 10-20wt% zinc nitrate solution of hydrogen, 1:0.5-1.5 is uniformly mixed by volume, is denoted as the first solution, spare；By copper,
The mass ratio of the sulfuric acid solution mixing of hydrogen peroxide, 20-30wt%, copper and hydrogen peroxide, sulfuric acid solution is 1:2-3:0.6-0.8.Instead
Solution is denoted as the second solution after answering, spare.
B) by two kinds of solution obtained above, 1-2:1 is mixed by volume, adds 0.5-1.5 times of swelling of solution quality
Soil is heated with stirring to 90-110 DEG C, stands 4-8h, dries, and reduction whitening powder is made；
C) reduction whitening powder is uniformly mixed in mass ratio for 1:1-2 with polyurethane foam solution, stand after curing successively into
Reduction brightening agent is made in row drying after crushing.
1) nonionic surfactant, amphoteric surfactant, marine algae extract are added in deionized water according to the ratio,
It is stirred evenly at 30 DEG C, obtains viscous solution.
Then plus acid-base modifier 2) sodium citrate, washing assisant are added into viscous solution, is uniformly dispersed at 35 DEG C,
PH value of solution is adjusted to 8.5 or so, then adds polymer overmold enzyme preparation, it is sour while adding polymer overmold enzyme preparation
Alkali regulator maintains pH value of solution 8.5 or so；Fabric washing liquid is made after mixing evenly.
Embodiment 2
A kind of fabric washing liquid of the enzyme preparation containing polymer overmold, comprising:
Ethoxylated fatty acid ester 15g,
Cocamidopropyl betaine 10g,
Polymer overmold enzyme preparation 1g,
Marine algae extract 0.1g,
Sodium citrate 0.1g,
Appropriate acid-base modifier,
Brightening agent 1g, softening agent 0.5g, essence 1g are restored,
Deionized water 70g.
A kind of preparation method of the fabric washing liquid of the enzyme preparation containing polymer overmold, comprising the following steps:
Polymer overmold enzyme preparation it is pre-prepared:
A 100g caprolactone is mixed with 2g benzyl alcohol, 1g stannous octoate), reacts 12h at 120 DEG C, will be reacted with chloroform
Product dissolution, then absolute methanol solution precipitates, and obtains the modified polycaprolactone of terminal hydroxy group；Take the modified polycaprolactone of 10g terminal hydroxy group
It is dissolved in chloroform, sequentially adds 0.5g 2- (dodecyl trithiocarbonic acid ester group) -2 Methylpropionic acid, 0.5g N- hydroxysuccinimidyl
Acid imide/dicyclohexylcarbodiimide, sufficiently after reaction, filtering, anhydrous methanol precipitation filtrates obtain polycaprolactone initiator.
B it) takes 100g lactide to mix with 1g benzyl alcohol, 0.5g stannous octoate, reacts 12h at 120 DEG C, it will be anti-with chloroform
Product is answered to dissolve, then absolute methanol solution precipitates, and obtains terminal hydroxy group polydactyl acid.
C it) takes 1g polycaprolactone initiator to be dissolved in dimethyl sulfoxide, 0.02g azodiisobutyronitrile is added, then adds 1g
Histidine polymerize 8h at 55 DEG C；0.5g terminal hydroxy group polydactyl acid, heat preservation polymerization 10h, with n-hexane to reaction solution are added again
Precipitating, obtains polymer.
D it) disperses 10g polymer in deionized water, adjusting pH is 7.2, adds 5g complex enzyme (alkali protease, alkalinity
Lipase, amylase), 30 DEG C are heated with stirring to, ultrasonic disperse is uniform, and after standing adsorption 2h, adjusting pH is 10, and dialysis obtains
The polymer overmold enzyme preparation that molecular weight is 8-12w, partial size is 100-500nm.
Restore the pre-prepared of brightening agent:
A) magnesium and zinc are dissolved in nitric acid solution respectively, the 10wt% magnesium nitrate solution containing hydrogen is made and contain hydrogen
The 10wt% zinc nitrate solution of gas, 1:0.5 is uniformly mixed by volume, is denoted as the first solution, spare；By copper, hydrogen peroxide,
The sulfuric acid solution of 20wt% mixes, and the mass ratio of copper and hydrogen peroxide, sulfuric acid solution is 1:3:0.0.8.Solution is denoted as after reaction
Two solution, it is spare.
B) by two kinds of solution obtained above, 1:1 is mixed by volume, is added 0.5 times of bentonite of solution quality, is stirred
It mixes and is heated to 90 DEG C, stand 8h, dry, reduction whitening powder is made；
C reduction whitening powder is uniformly mixed in mass ratio for 1:1 with polyurethane foam solution), is successively carried out after standing curing
Reduction brightening agent is made after dry, crushing.
1) nonionic surfactant, amphoteric surfactant, marine algae extract are added in deionized water according to the ratio,
It is stirred evenly at 30 DEG C, obtains viscous solution.
Then plus acid-base modifier 2) sodium citrate, washing assisant are added into viscous solution, is uniformly dispersed at 30 DEG C,
PH value of solution is adjusted to 9 or so, then adds polymer overmold enzyme preparation, soda acid while adding polymer overmold enzyme preparation
Regulator maintains pH value of solution 9 or so；Fabric washing liquid is made after mixing evenly.
Embodiment 3
A kind of fabric washing liquid of the enzyme preparation containing polymer overmold, comprising:
Alkanolamide 25g,
Dodecyl-dimethyl amine second lactone 5g,
Polymer overmold enzyme preparation 4g,
Marine algae extract 3g,
Sodium citrate 2g,
Appropriate acid-base modifier,
Brightening agent 1g, essence 1g, preservative 1g are restored,
Deionized water 60g.
A kind of preparation method of the fabric washing liquid of the enzyme preparation containing polymer overmold, comprising the following steps:
Polymer overmold enzyme preparation it is pre-prepared:
A 100g caprolactone is mixed with 4g benzyl alcohol, 2g stannous octoate), reacts 8h at 130 DEG C, will be reacted with chloroform
Product dissolution, then absolute methanol solution precipitates, and obtains the modified polycaprolactone of terminal hydroxy group；Take the modified polycaprolactone of 10g terminal hydroxy group
It is dissolved in chloroform, it is sub- to sequentially add 1g 2- (dodecyl trithiocarbonic acid ester group) -2 Methylpropionic acid, 1g N- hydroxysuccinimidyl acyl
Amine/dicyclohexylcarbodiimide, sufficiently after reaction, filtering, anhydrous methanol precipitation filtrates obtain polycaprolactone initiator.
B it) takes 100g lactide to mix with 2g benzyl alcohol, 1g stannous octoate, reacts 8h at 130 DEG C, will be reacted with chloroform
Product dissolution, then absolute methanol solution precipitates, and obtains terminal hydroxy group polydactyl acid.
C it) takes 1g polycaprolactone initiator to be dissolved in dimethyl sulfoxide, 0.05g azodiisobutyronitrile is added, then adds 3g
Histidine polymerize 4h at 65 DEG C；1.5g terminal hydroxy group polydactyl acid, heat preservation polymerization 6h, with n-hexane to reaction solution are added again
Precipitating, obtains polymer.
D it) disperses 10g polymer in deionized water, adjusting pH is 6, addition 15g complex enzyme (alkali protease, alkaline rouge
Fat enzyme, cellulase), 40 DEG C are heated with stirring to, ultrasonic disperse is uniform, and after standing adsorption 5h, adjusting pH is 10, and dialysis obtains
The polymer overmold enzyme preparation that molecular weight is 8-12w, partial size is 100-500nm.
Restore the pre-prepared of brightening agent:
A) magnesium and zinc are dissolved in nitric acid solution respectively, the 15wt% magnesium nitrate solution containing hydrogen is made and contain hydrogen
The 15wt% zinc nitrate solution of gas, 1:1 is uniformly mixed by volume, is denoted as the first solution, spare；By copper, hydrogen peroxide, 25wt%
Sulfuric acid solution mixing, copper and hydrogen peroxide, sulfuric acid solution mass ratio be 1:2.5:0.7.Solution is denoted as the second solution after reaction,
It is spare.
B) by two kinds of solution obtained above, 1.5:1 is mixed by volume, is added 1 times of bentonite of solution quality, is stirred
It mixes and is heated to 100 DEG C, stand 6h, dry, reduction whitening powder is made
C) reduction whitening powder is uniformly mixed in mass ratio for 1:1.5 with polyurethane foam solution, stand after curing successively into
Reduction brightening agent is made in row drying after crushing.
1) nonionic surfactant, amphoteric surfactant, marine algae extract are added in deionized water according to the ratio,
It is stirred evenly at 40 DEG C, obtains viscous solution.
Then plus acid-base modifier 2) sodium citrate, washing assisant are added into viscous solution, is uniformly dispersed at 40 DEG C,
PH value of solution is adjusted to 8.8, polymer overmold enzyme preparation is then added, with soda acid tune while adding polymer overmold enzyme preparation
Saving agent maintains pH value of solution 8.8；Fabric washing liquid is made after mixing evenly.
Embodiment 4
A kind of fabric washing liquid of the enzyme preparation containing polymer overmold, comprising:
Alkyl glycosides 25g,
Polymer overmold enzyme preparation 5g,
Marine algae extract 3g,
Sodium citrate 2g,
Appropriate acid-base modifier,
Brightening agent 1g, essence 1g, resist agent 1g are restored,
Deionized water 60g.
A kind of preparation method of the fabric washing liquid of the enzyme preparation containing polymer overmold, comprising the following steps:
Polymer overmold enzyme preparation it is pre-prepared:
A 100g caprolactone is mixed with 2.5g benzyl alcohol, 1.2g stannous octoate), reacts 9h at 120 DEG C, it will with chloroform
Reaction product dissolution, then absolute methanol solution precipitates, and obtains the modified polycaprolactone of terminal hydroxy group；The modification of 10g terminal hydroxy group is taken to gather oneself
Lactone is dissolved in chloroform, sequentially adds 0.6g 2- (dodecyl trithiocarbonic acid ester group) -2 Methylpropionic acid, 0.6g N- hydroxyl
Succinimide/dicyclohexylcarbodiimide, sufficiently after reaction, filtering, anhydrous methanol precipitation filtrates obtain polycaprolactone initiation
Agent.
B it) takes 100g lactide to mix with 1.2g benzyl alcohol, 0.6g stannous octoate, reacts 9h at 120 DEG C, it will with chloroform
Reaction product dissolution, then absolute methanol solution precipitates, and obtains terminal hydroxy group polydactyl acid.
C it) takes 1g polycaprolactone initiator to be dissolved in dimethyl sulfoxide, 0.01g azodiisobutyronitrile is added, then adds
1.5g histidine polymerize 5h at 60 DEG C；1g terminal hydroxy group polydactyl acid, heat preservation polymerization 9h, with n-hexane to reaction are added again
Liquid precipitate obtains polymer.
D it) disperses 10g polymer in deionized water, adjusting pH is 7, addition 8g complex enzyme (alkali protease, alkaline rouge
Fat enzyme), 35 DEG C are heated with stirring to, ultrasonic disperse is uniform, and after standing adsorption 5h, adjusting pH is 10, dialysis, and obtaining molecular weight is 8-
12w, the polymer overmold enzyme preparation that partial size is 100-500nm.
Restore the pre-prepared of brightening agent:
A) magnesium and zinc are dissolved in nitric acid solution respectively, the 15wt% magnesium nitrate solution containing hydrogen is made and contain hydrogen
The 15wt% zinc nitrate solution of gas, 1:1 is uniformly mixed by volume, is denoted as the first solution, spare；By copper, hydrogen peroxide, 25wt%
Sulfuric acid solution mixing, copper and hydrogen peroxide, sulfuric acid solution mass ratio be 1:2.5:0.7.Solution is denoted as the second solution after reaction,
It is spare.
B) by two kinds of solution obtained above, 1.5:1 is mixed by volume, is added 1 times of bentonite of solution quality, is stirred
It mixes and is heated to 100 DEG C, stand 6h, dry, reduction whitening powder is made
C) reduction whitening powder is uniformly mixed in mass ratio for 1:1.5 with polyurethane foam solution, stand after curing successively into
Reduction brightening agent is made in row drying after crushing.
1) nonionic surfactant, amphoteric surfactant, marine algae extract are added in deionized water according to the ratio,
It is stirred evenly at 35 DEG C, obtains viscous solution.
Then plus acid-base modifier 2) sodium citrate, washing assisant are added into viscous solution, is uniformly dispersed at 35 DEG C,
PH value of solution is adjusted to 8.5, polymer overmold enzyme preparation is then added, with soda acid tune while adding polymer overmold enzyme preparation
Saving agent maintains pH value of solution 8.5；Fabric washing liquid is made after mixing evenly.
Comparative example 1
A kind of fabric washing liquid of enzyme-containing formulation, comprising:
Fatty alcohol polyoxyethylene ether 35g,
Enzyme preparation 1g,
Sodium citrate 1g,
Appropriate acid-base modifier,
Brightening agent 1g, essence 1g,
Deionized water 58g.
Comparative example 2
A kind of fabric washing liquid of enzyme-containing formulation, comprising:
Fatty alcohol polyoxyethylene ether 35g,
Enzyme preparation 1g,
Marine algae extract 1g,
Sodium citrate 1g,
Appropriate acid-base modifier,
Brightening agent 1g, essence 1g,
Deionized water 57g.
Stability test
Stability test is carried out to the fabric washing liquid of embodiment 1-4 and comparative example 1-2: after 20 DEG C store 6 months, being seen
Product stable state is examined, as a result as follows:
| Group number | Clarify situation | Enzyme preparation settles situation |
| Embodiment 1 | It is not stratified, clarification, it is transparent | Without obvious sedimentation |
| Embodiment 2 | It is not stratified, clarification, it is transparent | Without obvious sedimentation |
| Embodiment 3 | It is not stratified, clarification, it is transparent | Without obvious sedimentation |
| Embodiment 4 | It is not stratified, clarification, it is transparent | Without obvious sedimentation |
| Comparative example 1 | It is not stratified, clarification, it is transparent | Bottom has obvious sediment |
| Comparative example 2 | It is not stratified, clarification, it is transparent | Bottom has part sediment |
By above data comparison it is found that the enzyme preparation in fabric detergent of the invention is not easily settled, and even if comparison
It is added with marine algae extract in example 2, also can not effectively avoid the sedimentation of enzyme preparation, and in the feelings of marine algae extract cooperation polymer
Under condition, it can effectively avoid.
Carry out high/low temperature stability test to the fabric washing liquid of embodiment 1-4 and comparative example 1-2: observation product stablizes shape
State is as a result as follows:
By above data comparison it is found that the enzyme preparation in fabric detergent of the invention is not easily settled, and seaweed is extracted
The addition of object can only have certain anti-settling effect at normal temperature, and effect is unobvious under high/low temperature.
In addition, there are many gold for dispersion in the reduction brightening agent also containing reduction brightening agent in washing powder in embodiment 1-4
Belong to ion, forms galvanic effect due to the potential difference of several metals in water environment (after washing powder investment water) middle meeting；Again
Hydrogen in cooperation reduction brightening agent in load, has extremely strong reproducibility, can go back to the fabric for being oxidized and turning to be yellow
Original, makes it restore original white, and whitening effect is preferable.
In its preparation process, in step A), first be made containing hydrogen, magnesium, zinc ion the first solution；In preparation second
When solution, the activity of copper is lower than hydrogen, can not directly react with hydrogen peroxide, for this purpose, the present invention by copper be added to strongly acidic solution+
In dioxygen water environment, copper is oxidized in this Strong oxdiative environment, generates copper sulphate.In step B), two kinds of solution are mixed, and
Add bentonite, bentonite have outstanding adsorptivity and cation exchange capacity (CEC), can by solution metal ion and
A small amount of hydrogen successfully loads thereon.In step C), reduction whitening powder is further carried on polyurethane foam solution, into
After the curing of one step is dry, the rigid foam particle that mushy load has reduction whitening powder, i.e. reduction brightening agent are formed.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (10)
1. a kind of fabric washing liquid of enzyme preparation containing polymer overmold, it is characterised in that comprise the following components in parts by weight:
15-35 parts of nonionic surfactant,
0-10 parts of amphoteric surfactant,
0.5-5 parts of polymer overmold enzyme preparation,
0.1-3 parts of marine algae extract,
0.1-5 parts of sodium citrate,
0-5 parts of acid-base modifier,
0.1-10 parts of washing assisant,
40-80 parts of deionized water.
2. a kind of fabric washing liquid of the enzyme preparation containing polymer overmold as described in claim 1, which is characterized in that it is described it is non-from
Sub- surfactant in fatty alcohol polyoxyethylene ether, ethoxylated fatty acid ester, alkanolamide and alkyl glycosides at least
It is a kind of.
3. a kind of fabric washing liquid of the enzyme preparation containing polymer overmold as described in claim 1, which is characterized in that the both sexes
Surfactant is selected from least one of cocamidopropyl betaine, dodecyl-dimethyl amine second lactone.
4. a kind of fabric washing liquid of the enzyme preparation containing polymer overmold as described in claim 1, which is characterized in that the polymerization
It is the complex enzyme by polymer overmold that object, which coats enzyme preparation,.
5. a kind of fabric washing liquid of the enzyme preparation containing polymer overmold as claimed in claim 4, which is characterized in that described compound
Enzyme in alkali protease, alkaline lipase, amylase and cellulase at least two.
6. a kind of fabric washing liquid of the enzyme preparation containing polymer overmold as described in claim 4 or 5, which is characterized in that described
Polymer overmold enzyme preparation the preparation method is as follows:
A 100 parts of caprolactones are mixed with 2-4 parts of benzyl alcohols, 1-2 parts of stannous octoates), 8-12h is reacted at 120-130 DEG C, are used
Chloroform dissolves reaction product, and then absolute methanol solution precipitates, and obtains the modified polycaprolactone of terminal hydroxy group；10 parts of terminal hydroxy groups are taken to change
Property polycaprolactone is dissolved in chloroform, sequentially add 0.5-1 parts of 2- (dodecyl trithiocarbonic acid ester group) -2 Methylpropionic acid,
0.5-1 parts of n-hydroxysuccinimide/dicyclohexylcarbodiimides, sufficiently after reaction, filtering, anhydrous methanol precipitation filtrates are obtained
To polycaprolactone initiator；
B it) takes 100 parts of lactides to mix with 1-2 parts of benzyl alcohols, 0.5-1 parts of stannous octoates, reacts 8-12h at 120-130 DEG C,
Reaction product is dissolved with chloroform, then absolute methanol solution precipitates, and obtains terminal hydroxy group polydactyl acid；
C it) takes 1 part of polycaprolactone initiator to be dissolved in dimethyl sulfoxide, 0.01-0.05 parts of azodiisobutyronitriles is added, then add
Add 1-3 parts of histidines, polymerize 4-8h at 55-65 DEG C；0.5-1.5 parts of terminal hydroxy group polydactyl acids, heat preservation polymerization 6- are added again
10h obtains polymer with n-hexane to reaction liquid precipitate；
D it) disperses 10 parts of polymer in deionized water, tune pH is 6-7.5, adds 5-15 parts of complex enzymes, is heated with stirring to 30-
40 DEG C, ultrasonic disperse is uniform, after standing adsorption 2-6h, adjusts pH and is greater than 8, dialysis obtains polymer overmold enzyme preparation；
Above-mentioned substance number is parts by weight.
7. a kind of fabric washing liquid of the enzyme preparation containing polymer overmold as claimed in claim 6, which is characterized in that the polymerization
The molecular weight of object is 8-12w.
8. a kind of fabric washing liquid of the enzyme preparation containing polymer overmold as claimed in claim 6, which is characterized in that the polymerization
The partial size that object coats enzyme preparation is 100-500nm.
9. a kind of fabric washing liquid of the enzyme preparation containing polymer overmold as described in claim 1, which is characterized in that the washing
Auxiliary agent is selected from least one of brightening agent, softening agent, essence, pigment, preservative and resist agent.
10. a kind of preparation method of the fabric washing liquid of the enzyme preparation containing polymer overmold as described in claim 1, it is characterised in that
The following steps are included:
1) nonionic surfactant, amphoteric surfactant, marine algae extract are added in deionized water according to the ratio,
It is stirred evenly at 30-40 DEG C, obtains viscous solution；
Then plus acid-base modifier 2) sodium citrate, washing assisant are added into viscous solution, is uniformly dispersed at 30-40 DEG C,
PH value of solution is adjusted to 8-10, then adds polymer overmold enzyme preparation, soda acid while adding polymer overmold enzyme preparation
Regulator maintains pH value of solution in 8-10；Fabric washing liquid is made after mixing evenly.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109666547A (en) * | 2018-12-17 | 2019-04-23 | 福州立洁生物科技有限公司 | A kind of Antibiotic liquid detergent and preparation method thereof |
| CN109679786A (en) * | 2018-12-17 | 2019-04-26 | 福州立洁生物科技有限公司 | A kind of preparation method of detergent particles |
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| CN1656205A (en) * | 2002-07-01 | 2005-08-17 | 诺和酶股份有限公司 | Stabilization of granules |
| CN106635495A (en) * | 2016-12-09 | 2017-05-10 | 苏州纳贝通环境科技有限公司 | Antibacterial hand-protective hand-wash liquid detergent and preparation method thereof |
| CN107955725A (en) * | 2017-12-27 | 2018-04-24 | 肖国华 | A kind of seaweed liquid detergent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1656205A (en) * | 2002-07-01 | 2005-08-17 | 诺和酶股份有限公司 | Stabilization of granules |
| CN106635495A (en) * | 2016-12-09 | 2017-05-10 | 苏州纳贝通环境科技有限公司 | Antibacterial hand-protective hand-wash liquid detergent and preparation method thereof |
| CN107955725A (en) * | 2017-12-27 | 2018-04-24 | 肖国华 | A kind of seaweed liquid detergent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109666547A (en) * | 2018-12-17 | 2019-04-23 | 福州立洁生物科技有限公司 | A kind of Antibiotic liquid detergent and preparation method thereof |
| CN109679786A (en) * | 2018-12-17 | 2019-04-26 | 福州立洁生物科技有限公司 | A kind of preparation method of detergent particles |
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