A kind of instant capacity peroxidating high-molecular copolymer pasteurization material
Technical field
Disappear the present invention relates to water-soluble high-molecular material field, more particularly to a kind of instant capacity peroxidating high-molecular copolymer
Malicious material.
Background technology
Used as traditional pasteurization material, chlorine-containing disinfecting material effects mechanism is hydrolysis generation hypochlorous acid molecule, using secondary chlorine
The oxidation sterilizing of acid molecule.But use chlorine-containing disinfectant sterilize when, by hypochlorous acid molecule HCIO decomposite time
Chlorate ions (OCL-), easily forms carcinogen chloroform (CHCL with impurities in water3) or trichlorophenol, so seldom making now
Carried out disinfection with chlorine-containing disinfectant, and generally use peroxide sterilants.
Peroxide sterilants have Strong oxdiative ability, and various microorganisms are very sensitive to it, can kill all microorganisms
Go out.This kind of disinfectant is including hydrogen peroxide, Peracetic acid, chlorine dioxide and ozone etc..Their advantage is in article after sterilizing
On leave no residue toxicity, non-carcinogenesis.Someone is researched and produced disinfectants with rich carboxylic macromolecular material in recent years, such as:
Peroxidating acrylic acid (sodium salt), peroxidating maleic acid (sodium salt), methyl acrylic acid (sodium salt) and peroxidating fumaric acid (sodium
Salt), but above-mentioned peroxidating macromolecule pasteurization material all has a problem that to be exactly slow dissolution velocity, is difficult dispersion, causes to make
Used time is very inconvenient.It is pointed out that peroxidating macromolecular material can not typically be used in oil-soluble system.
At present, peroxidating macromolecule pasteurization material product is mostly in solid powder state, although have good water solubility, but
It is in use, because product water solubility is very good, one layer of hydration shell to be combined to form with water at once after being immersed in the water, high score
Sub- pasteurization material is wrapped up, and is combined with water so as to hinder the molecule inside macromolecule material particle, it is apparent on be formed
White " bubble " one by one is named " flake ".Flake is once formed will greatly prolong the time of disinfectant.
There is substantial amounts of technology in the prior art for eliminating flake, substantially realize copolymerization by adding dispersion aids
In thing fish-eye number reduction (such as CN102471508A, CN1335859A, CN1813004A, CN1515595A,
CN103788305A etc.), however, not yet having document report for enabling macromolecule pasteurization material rapid dispersion, being dissolved in water
In can eliminate the technology of " flake ", especially peroxidating macromolecule pasteurization material.
On the other hand, from molecular structure, substantial amounts of hydrophilic carboxyl, institute are contained in peroxidating macromolecular material
So that the disinfectant is difficult to apply in oleaginous system.How the compatibility of macromolecule pasteurization material and oil-soluble system is solved
It is the problem for needing to solve.
The content of the invention
In view of the above problems, peroxidating macromolecule material can be solved by eliminating flake present invention aim at offer one kind
Expect that the dispersing and dissolving speed for existing is excessively slow and can be used under oil soluble system as the instant capacity peroxide of macromolecule disinfectant
Change high-molecular copolymer pasteurization material.
Specifically, the present invention provides a kind of instant capacity peroxidating high-molecular copolymer pasteurization material, it is characterised in that:It is described
Peroxide macromolecular material contains following group:
Wherein, M is H or metal ion.Meanwhile, the alkyl of certain chain length, chain alkyl matter are also contained in Polymer Structure
Amount number accounts for the 0.1-15% of molecular weight sum.
According to the above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material of the present invention, it is characterised in that:The peroxide
Change high-molecular copolymer pasteurization material, can by the monomeric compound containing at least one double bond and at least one carboxyl simultaneously,
Such as:Acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid etc., and different chain length unsaturated monomer by combined polymerization
The polymer copolymerization compound of alkyl of the polymerisation generation accordingly containing a large amount of carboxyls and different chain length, the polymer passes through again
Peroxidization generates corresponding peroxide macromolecule pasteurization material, and the pasteurization material can also generate phase by neutralization reaction
The peroxide salt answered.
According to the above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material of the present invention, it is characterised in that:It is described not
Saturation monomer can be that the esters of unsaturated carboxylic acids for closing reaction, unsaturated alkane can be copolymerized with above-mentioned carboxylic unsaturated carboxylic acid
One or several of hydrocarbon, unsaturated aromatic hydrocarbon derivative, unsaturated halogenated hydrocarbons or unsaturation ring alkane derivatives.
According to the above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material of the present invention, it is characterised in that:The peroxide
Change high-molecular copolymer pasteurization material, it is also possible to directly with the commercially available macromolecule material through alkyl modified containing a large amount of carboxyls
Material, such as:It is alkyl-modified polyacrylic acid and its various salt, alkyl-modified polymethylacrylic acid and its various salt, alkyl-modified
HPMA and its various salt, alkyl-modified poly- itaconic acid and its various salt etc., directly prepared by peroxidization
Form corresponding peroxide macromolecule pasteurization material.
According to the above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material of the present invention, it is characterised in that:The peroxide
Change high-molecular copolymer pasteurization material, can be the form of solid, liquid and any convenient use.
According to the above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material of the present invention, it is characterised in that:The peroxide
Change high-molecular copolymer pasteurization material, can directly use, it is also possible to be prepared into corresponding disinfectant products with other chemicals
And use, such as colloid or lotion etc..
According to the above-mentioned instant capacity macromolecule pasteurization material of the present invention, commercially available poly carboxyl family macromolecule material can also be used
Material carries out hydrophobically modified preparation by esterification to macromolecular material.
Such as:With commercial polypropylene acid in the presence of p-methyl benzenesulfonic acid in toluene solvant, with lauryl alcohol reaction, also may be used
To form alkyl-modified polyacrylic acid, then again and hydroperoxidation, alkyl-modified peroxidating polyacrylic acid is formed.
According to the present invention, by the copolymerization of carboxylic acid type monomer and non-carboxylic acid class monomer, alkyl is carried out to polycarboxylic acid's molecule
Change and be modified, increased the hydrophobicity of polycarboxylic acid's molecule so that macromolecular material increased dissolution velocity.
According to the present invention, due to introducing peroxy-radical in instant macromolecule, flake is effectively eliminated, it is possible to forming speed
Soluble macromolecular pasteurization material.
, according to the invention it is preferred to using pasteurization material based on peroxidating acrylic polymer pasteurization material, because
Peroxidating acrylic polymer pasteurization material compared to other organic peroxides, with peroxy radicals ratio higher,
And the product polypropylene acid for having sterilized later is the food additives that a kind of state food is allowed safely.So, such as peroxidating
Acrylic polymer peroxide sterilants have obvious advantage in the sterilization as contact food:Nontoxic, harmless, nothing
Secondary pollution and edible.Past this kind of product is more long due to dissolution time, there are problems that flake so that when using very not
It is convenient.The peroxidating macromolecular material that the present invention is prepared by carrying out hydrophobically modified to macromolecular chain, overcomes dispersing and dissolving
Slow not enough problem.
Specific embodiment
The present invention is explained in detail below for specific embodiment.
The present invention provides a kind of instant capacity peroxidating high-molecular copolymer pasteurization material, it is characterised in that:The peroxidating
Thing macromolecular material contains following group:
Wherein, M is H or metal ion.Meanwhile, the alkyl of certain chain length, chain alkyl matter are also contained in Polymer Structure
Amount number accounts for the 0.1-15% of molecular weight sum.
According to above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material, it is characterised in that:The peroxidating high score
Sub- copolymer pasteurization material, can be by the monomeric compound containing at least one double bond and at least one carboxyl simultaneously, such as:Propylene
Acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid etc., and the unsaturated monomer of different chain length are anti-by combined polymerization polymerization
The polymer copolymerization compound of the alkyl accordingly containing a large amount of carboxyls and different chain length should be generated, the polymer is again by peroxidating
The corresponding peroxide macromolecule pasteurization material of reaction generation, the pasteurization material can also generate corresponding mistake by neutralization reaction
Oxide salt.
According to above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material, it is characterised in that:Described unsaturation is single
Body can be copolymerized to close the esters of unsaturated carboxylic acids of reaction, unsaturated alkane, no with above-mentioned carboxylic unsaturated carboxylic acid
One or several of saturation aromatic hydrocarbon derivative, unsaturated halogenated hydrocarbons or unsaturation ring alkane derivatives.
According to above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material, it is characterised in that:The peroxidating high score
Sub- copolymer pasteurization material, it is also possible to directly with the commercially available macromolecular material through alkyl modified containing a large amount of carboxyls, such as:Alkane
The modified polyacrylic acid of base and its various salt, alkyl-modified polymethylacrylic acid and its various salt, alkyl-modified poly- Malaysia
Acid anhydrides and its various salt, alkyl-modified poly- itaconic acid and its various salt etc., are directly prepared from corresponding by peroxidization
Peroxide macromolecule pasteurization material.
According to above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material, it is characterised in that:The peroxidating high score
Sub- copolymer pasteurization material, can be the form of solid, liquid and any convenient use.
According to above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material, it is characterised in that:The peroxidating high score
Sub- copolymer pasteurization material, can directly use, it is also possible to be prepared into corresponding disinfectant products with other chemicals and use,
Such as colloid or lotion etc..
According to the present invention, by the copolymerization of carboxylic acid type monomer and non-carboxylic acid class monomer, alkyl is carried out to polycarboxylic acid's molecule
Change and be modified, increased the hydrophobicity of polycarboxylic acid's molecule so that macromolecular material increased dissolution velocity.
According to the present invention, due to introducing peroxy-radical in instant macromolecule, flake is effectively eliminated, it is possible to forming speed
Soluble macromolecular pasteurization material.
, according to the invention it is preferred to using pasteurization material based on peroxidating acrylic polymer pasteurization material, because
Peroxidating acrylic polymer pasteurization material compared to other organic peroxides, with peroxy radicals ratio higher,
And the product polypropylene acid for having sterilized later is the food additives that a kind of state food is allowed safely.So, such as peroxidating
Acrylic polymer peroxide sterilants have obvious advantage in the sterilization as contact food:Nontoxic, harmless, nothing
Secondary pollution and edible.Past this kind of product is more long due to dissolution time, there are problems that flake so that when using very not
It is convenient.The peroxidating macromolecular material that the present invention is prepared by carrying out hydrophobically modified to macromolecular chain, overcomes dispersing and dissolving
Slow not enough problem.
Embodiment 1:
Instant capacity high-molecular copolymer pasteurization material of the invention is made by the steps:
1, the preparation of monomer solution:The addition 2g octadecyl methacrylates in the beaker of 500ml, 6g ethyl acrylates,
92g acrylic acid, with 1:1 ethyl acetate and the mixed solution constant volume of hexamethylene are made monomer solution to 250ml;
2, the preparation of initiator solution:The own ester of 0.4g diethyl dioxides is added in the beaker of 100ml, 20ml1 is added:
1 ethyl acetate and the mixed solution of hexamethylene, are configured to initiator solution.
3, the high molecular synthesis of instant capacity:
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
600ml1:1 ethyl acetate and the mixed solution of hexamethylene and 80ml monomer solutions, are passed through nitrogen 30min, are then heated to
50C°.Add initiator solution 10ml, keeping temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid, 2-3 hours completion of dropping.Remaining initiator solution is added system, continues to react 3 hours.Room temperature is reduced the temperature to, is gone out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
The above-mentioned instant macromolecules of 100g, 600ml mixed solvents cool to 5C ° or so, start that 50% hydrogen peroxide 100g is added dropwise.2-3 is small
When completion of dropping.Stop refrigeration, continue to react 8 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
Embodiment 2:
Instant capacity high-molecular copolymer pasteurization material of the invention is made by the steps:
1, the preparation of monomer solution:8g ethyl acrylates, 3g tert-butyl acrylates, 89g third are added in the beaker of 500ml
Olefin(e) acid, with 1:1 ethyl acetate and the mixed solution constant volume of hexamethylene are made monomer solution to 250ml;
2, the preparation of initiator solution:The own ester of 0.4g diethyl dioxides is added in the beaker of 100ml, 20ml1 is added:
1 ethyl acetate and the mixed solution of hexamethylene, are configured to initiator solution.
3, the high molecular synthesis of instant capacity:
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
600ml1:1 ethyl acetate and the mixed solution of hexamethylene and 80ml monomer solutions, are passed through nitrogen 30min, are then heated to
50C°.Add initiator solution 10ml, keeping temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid, 2-3 hours completion of dropping.Remaining initiator solution is added system, continues to react 3 hours.Room temperature is reduced the temperature to, is gone out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
The above-mentioned instant macromolecules of 100g, 600ml mixed solvents cool to 0C ° or so, start that 50% hydrogen peroxide 80g is added dropwise.2-3 is small
When completion of dropping.Stop refrigeration, continue to react 8 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
Embodiment 3
Instant capacity high-molecular copolymer pasteurization material of the invention is made by the steps:
1, the preparation of monomer solution:2g lauryl methacrylates, 6g i-butyls are added in the beaker of 500ml
Ester, 92g methacrylic acids, with 1:1 ethyl acetate and the mixed solution constant volume of hexamethylene are made monomer solution to 250ml;
2, the preparation of initiator solution:The own ester of 0.4g diethyl dioxides is added in the beaker of 100ml, 20ml1 is added:
1 ethyl acetate and the mixed solution of hexamethylene, are configured to initiator solution.
3, the high molecular synthesis of instant capacity:
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
600ml1:1 ethyl acetate and the mixed solution of hexamethylene and 80ml monomer solutions, are passed through nitrogen 30min, are then heated to
50C°.Add initiator solution 10ml, keeping temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid, 2-3 hours completion of dropping.Remaining initiator solution is added system, continues to react 3 hours.Room temperature is reduced the temperature to, is gone out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
The above-mentioned instant macromolecules of 100g, 600ml mixed solvents cool to 5C ° or so, start that 50% hydrogen peroxide 100g is added dropwise.2-3 is small
When completion of dropping.Stop refrigeration, continue to react 8 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
Embodiment 4
Instant capacity high-molecular copolymer pasteurization material of the invention is made by the steps:
1, the preparation of monomer solution:2g lauryl methacrylates, 10g styrene, 88g are added in the beaker of 500ml
Methacrylic acid, with 1:1 ethyl acetate and the mixed solution constant volume of hexamethylene are made monomer solution to 250ml;
2, the preparation of initiator solution:The own ester of 0.4g diethyl dioxides is added in the beaker of 100ml, 20ml1 is added:
1 ethyl acetate and the mixed solution of hexamethylene, are configured to initiator solution.
3, the high molecular synthesis of instant capacity:
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
600ml1:1 ethyl acetate and the mixed solution of hexamethylene and 80ml monomer solutions, are passed through nitrogen 30min, are then heated to
50C°.Add initiator solution 10ml, keeping temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid, 2-3 hours completion of dropping.Remaining initiator solution is added system, continues to react 3 hours.Room temperature is reduced the temperature to, is gone out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
The above-mentioned instant macromolecules of 100g, 600ml mixed solvents cool to 10C ° or so, start that 50% hydrogen peroxide 120g is added dropwise.2-3
Hour completion of dropping.Stop refrigeration, continue to react 8 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
Embodiment 5
Instant capacity high-molecular copolymer pasteurization material of the invention is made by the steps:
1, the preparation of monomer solution:The addition 5g EHMAs in the beaker of 500ml, 8g butyl acrylates,
87g acrylic acid, with 1:1 ethyl acetate and the mixed solution constant volume of hexamethylene are made monomer solution to 250ml;
2, the preparation of initiator solution:The own ester of 0.4g diethyl dioxides is added in the beaker of 100ml, 20ml1 is added:
1 ethyl acetate and the mixed solution of hexamethylene, are configured to initiator solution.
3, the high molecular synthesis of instant capacity:
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
600ml1:1 ethyl acetate and the mixed solution of hexamethylene and 80ml monomer solutions, are passed through nitrogen 30min, are then heated to
50C°.Add initiator solution 10ml, keeping temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid, 2-3 hours completion of dropping.Remaining initiator solution is added system, continues to react 3 hours.Room temperature is reduced the temperature to, is gone out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
The above-mentioned instant macromolecules of 100g, 600ml mixed solvents cool to 5C ° or so, start that 30% hydrogen peroxide 210g is added dropwise.2-3 is small
When completion of dropping.Stop refrigeration, continue to react 8 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
Embodiment 6
Instant capacity high-molecular copolymer pasteurization material of the invention is made by the steps:
1, the preparation of monomer solution:2g butyl maleates, 6g dimethyl maleates, 92g are added in the beaker of 500ml
Methacrylic acid, with 1:1 ethyl acetate and the mixed solution constant volume of hexamethylene are made monomer solution to 250ml;
2, the preparation of initiator solution:The own ester of 0.4g diethyl dioxides is added in the beaker of 100ml, 20ml1 is added:
1 ethyl acetate and the mixed solution of hexamethylene, are configured to initiator solution.
3, the high molecular synthesis of instant capacity:
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
600ml1:1 ethyl acetate and the mixed solution of hexamethylene and 80ml monomer solutions, are passed through nitrogen 30min, are then heated to
50C°.Add initiator solution 10ml, keeping temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid, 2-3 hours completion of dropping.Remaining initiator solution is added system, continues to react 3 hours.Room temperature is reduced the temperature to, is gone out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
The above-mentioned instant macromolecules of 100g, 600ml mixed solvents cool to 15C ° or so, start that 40% hydrogen peroxide 180g is added dropwise.2-3
Hour completion of dropping.Stop refrigeration, continue to react 16 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
Instant capacity macromolecule pasteurization material of the invention, can also pass through ester with commercially available poly carboxyl family macromolecule material
Change reaction, hydrophobically modified preparation is carried out to macromolecular material.Step is as follows:
Embodiment 7
In equipped with mechanical agitator, water knockout drum, the 1000ml there-necked flasks of thermometer, 100g commercial polypropylenes are added
Acid, 3g p-methyl benzenesulfonic acids and 8.0g laruyl alcohols, last solubilizer toluene.150 DEG C of backflows, Zhi Daofen are warmed up under strong agitation
There is no water droplet to form reaction in hydrophone to terminate.400 mesh filter cloth centrifugal filtrations, remove solvent, 85 DEG C of vacuum drying.Obtain yellowish white
Pulverulent solids.
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
The above-mentioned instant macromolecules of 100g, 600ml mixed solvents cool to 5C ° or so, start that 50% hydrogen peroxide 90g is added dropwise.2-3 is small
When completion of dropping.Stop refrigeration, continue to react 10 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
Embodiment 8
In equipped with mechanical agitator, water knockout drum, the 1000ml there-necked flasks of thermometer, 100g commercial polypropylenes are added
Acid, 6g p-methyl benzenesulfonic acids and the 10.0g tert-butyl alcohols, last solubilizer benzene.110 DEG C of backflows, Zhi Daofen are warmed up under strong agitation
There is no water droplet to form reaction in hydrophone to terminate.400 mesh filter cloth centrifugal filtrations, remove solvent, 85 DEG C of vacuum drying.Obtain yellowish white
Pulverulent solids.
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
The above-mentioned instant macromolecules of 100g, 600ml mixed solvents cool to 5C ° or so, start that 35% hydrogen peroxide 130g is added dropwise.2-3 is small
When completion of dropping.Stop refrigeration, continue to react 10 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
Embodiment 9
In equipped with mechanical agitator, water knockout drum, the 1000ml there-necked flasks of thermometer, 100g commercial polypropylenes are added
Acid, 3g p-methyl benzenesulfonic acids and 12.0g isobutanols, last solubilizer toluene.150 DEG C of backflows are warmed up under strong agitation, until
There is no water droplet to form reaction in water knockout drum to terminate.400 mesh filter cloth centrifugal filtrations, remove solvent, 85 DEG C of vacuum drying.Obtain micro- yellowish-white
Color pulverulent solids.
In the 1L four-hole boiling flasks equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnels, add
The above-mentioned instant macromolecules of 100g, 600ml mixed solvents cool to 5C ° or so, start that 50% hydrogen peroxide 90g is added dropwise.2-3 is small
When completion of dropping.Stop refrigeration, continue to react 10 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
In sum, the present invention is described in detail by specific embodiment, but the explanation be it is exemplary,
Those skilled in the art can on its basis carry out various changes and modifications, without departing from present inventive concept and spirit, this
A little changes and modification all should fall under the scope of the present invention, and the scope of the present invention is defined by the following claims.