A kind of instant capacity peroxidating high-molecular copolymer pasteurization material
Technical field
The present invention relates to water-soluble high-molecular material fields more particularly to a kind of instant capacity peroxidating high-molecular copolymer to disappear
Malicious material.
Background technique
As traditional pasteurization material, chlorine-containing disinfecting material effects mechanism is that hydrolysis generates hypochlorous acid molecule, utilizes secondary chlorine
The oxidation sterilizing of acid molecule.But when chlorine-containing disinfectant being used to sterilize, decomposited by hypochlorous acid molecule HCIO secondary
Chlorate ions (OCL-) easily form carcinogen chloroform (CHCL with impurities in water3) or trichlorophenol, so seldom making now
It is carried out disinfection with chlorine-containing disinfectant, and generallys use peroxide sterilants.
Peroxide sterilants have Strong oxdiative ability, and various microorganisms are very sensitive to it, can kill all microorganisms
It goes out.This kind of disinfectant includes hydrogen peroxide, Peracetic acid, chlorine dioxide and ozone etc..They the advantages of are after sterilizing in article
On leave no residue toxicity, non-carcinogenesis.Someone is researched and produced disinfectants with rich carboxylic high molecular 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 be exactly that solution rate is slow, is not easy to disperse, causes to make
Used time is very inconvenient.It should be pointed out that peroxidating high molecular material cannot generally be used in oil-soluble system.
Currently, peroxidating macromolecule pasteurization material product is mostly in solid powder state, although there is good water solubility,
It is in use, since product water solubility is very good, one layer of hydration shell to be formed in conjunction with water at once after being immersed in the water, high score
Sub- pasteurization material wraps up, to hinder molecule inside macromolecule material particle in conjunction with water, is apparently formed
It " bubble " of white one by one or cries " flake ".Flake will greatly prolong the time of disinfectant once being formed.
A large amount of technology exists in the prior art for eliminating flake, copolymerization is substantially realized by addition dispersion aids
In object fish-eye number reduction (such as CN102471508A, CN1335859A, CN1813004A, CN1515595A,
CN103788305A etc.), however, there has been no document reports 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, a large amount of hydrophilic carboxyl, institute are contained in peroxidating high molecular material
With the disinfectant is difficult to apply in oleaginous system.How the compatibility of macromolecule pasteurization material Yu oil-soluble system is solved
It is problem to be solved.
Summary of the invention
In view of the above problems, it is an object of that present invention to provide one kind to solve peroxidating macromolecule material by eliminating flake
Expect that existing dispersing and dissolving speed is excessively slow and is able to use the instant capacity peroxide as macromolecule disinfectant under oily solution system
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: described
Peroxide high molecular material contains following group:
Wherein, M is H or metal ion.Meanwhile also containing the alkyl of certain chain length, chain alkyl matter in Polymer Structure
Amount number accounts for the 0.1-15% of molecular weight sum.
Above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material according to the present invention, it is characterised in that: the peroxide
Change high-molecular copolymer pasteurization material, can by the monomeric compound simultaneously containing at least one double bond He at least one carboxyl,
Such as: acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid and the unsaturated monomer of different chain length pass through combined polymerization
The polymer copolymerization that polymerization reaction generates the alkyl containing a large amount of carboxyls and different chain length accordingly closes object, the polymer using
Peroxidization generates corresponding peroxide macromolecule pasteurization material, which can also generate phase by neutralization reaction
The peroxide salt answered.
Above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material according to the present invention, it is characterised in that: it is described not
Saturation monomer, which can be to be copolymerized with above-mentioned carboxylic unsaturated carboxylic acid, closes the esters of unsaturated carboxylic acids reacted, unsaturated alkane
The one or several kinds of hydrocarbon, unsaturated aromatic hydrocarbon derivative, unsaturated halogenated hydrocarbons or unsaturated ring alkane derivatives.
Above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material according to the present invention, it is characterised in that: the peroxide
Change high-molecular copolymer pasteurization material, the macromolecule material through alkyl modified that can also directly with commercially available containing a large amount of carboxyls
Material, such as: alkyl-modified polyacrylic acid and its various salt, alkyl-modified polymethylacrylic acid and its various salt, alkyl-modified
Polymaleic anhydride and its various salt, alkyl-modified poly- itaconic acid and its various salt etc., directly prepared by peroxidization
Into corresponding peroxide macromolecule pasteurization material.
Above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material according to the present invention, it is characterised in that: the peroxide
Change high-molecular copolymer pasteurization material, can be solid, liquid and form arbitrarily convenient to use.
Above-mentioned instant capacity peroxidating high-molecular copolymer pasteurization material according to the present invention, it is characterised in that: the peroxide
Change high-molecular copolymer pasteurization material, can directly use, corresponding disinfectant products can also be prepared into other chemicals
And it uses, such as colloid or lotion etc..
Above-mentioned instant capacity macromolecule pasteurization material according to the present invention can also use commercially available poly carboxyl class macromolecule material
Material carries out hydrophobically modified preparation by esterification, to high molecular material.
Such as: it in the presence of p-methyl benzenesulfonic acid, is reacted with lauryl alcohol in toluene solvant with commercial polypropylene acid, it can also
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, the hydrophobicity of polycarboxylic acid's molecule is increased, so that high molecular material increases solution rate.
According to the present invention, due to introducing peroxy-radical in instant macromolecule, flake is effectively eliminated, so being capable of forming speed
Soluble macromolecular pasteurization material.
, according to the invention it is preferred to using peroxidating acrylic polymer pasteurization material as basic pasteurization material, because
Peroxidating acrylic polymer pasteurization material is compared to other organic peroxides, peroxy radicals ratio with higher,
And having sterilized later product polypropylene acid is a kind of food additives that state food allows safely.So such as peroxidating
Acrylic polymer peroxide sterilants have apparent advantage: nontoxic, harmless, nothing in the disinfection as contact food
Secondary pollution and edible.There is flake since dissolution time is longer in past this kind of product, so that when using very not
It is convenient.The peroxidating high molecular material that the present invention is prepared and carrying out hydrophobically modified to macromolecular chain, overcomes dispersing and dissolving
Slow insufficient 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
Object high molecular material contains following group:
Wherein, M is H or metal ion.Meanwhile also containing the alkyl of certain chain length, chain alkyl matter 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 simultaneously containing at least one double bond He at least one carboxyl, 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 that the alkyl accordingly containing a large amount of carboxyls and different chain length should be generated closes object, and the polymer is using peroxidating
Reaction generates corresponding peroxide macromolecule pasteurization material, which 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: the unsaturation is single
Body, which can be to be copolymerized with above-mentioned carboxylic unsaturated carboxylic acid, closes esters of unsaturated carboxylic acids react, unsaturation alkane, no
It is saturated the one or several kinds of aromatic hydrocarbon derivative, unsaturated halogenated hydrocarbons or unsaturated 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, can also be directly with the commercially available high molecular material through alkyl modified containing a large amount of carboxyls, such as: alkane
Base modified polyacrylic acid 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 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 solid, liquid and form arbitrarily convenient to 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, and can also 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, the hydrophobicity of polycarboxylic acid's molecule is increased, so that high molecular material increases solution rate.
According to the present invention, due to introducing peroxy-radical in instant macromolecule, flake is effectively eliminated, so being capable of forming speed
Soluble macromolecular pasteurization material.
, according to the invention it is preferred to using peroxidating acrylic polymer pasteurization material as basic pasteurization material, because
Peroxidating acrylic polymer pasteurization material is compared to other organic peroxides, peroxy radicals ratio with higher,
And having sterilized later product polypropylene acid is a kind of food additives that state food allows safely.So such as peroxidating
Acrylic polymer peroxide sterilants have apparent advantage: nontoxic, harmless, nothing in the disinfection as contact food
Secondary pollution and edible.There is flake since dissolution time is longer in past this kind of product, so that when using very not
It is convenient.The peroxidating high molecular material that the present invention is prepared and carrying out hydrophobically modified to macromolecular chain, overcomes dispersing and dissolving
Slow insufficient 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 methacrylate in the beaker of 500ml, 6g ethyl acrylate,
Monomer solution is made with the ethyl acetate of 1:1 and the mixed solution constant volume of hexamethylene to 250ml in 92g acrylic acid;
2, the preparation of initiator solution: being added the own ester of 0.4g diethyl dioxide in the beaker of 100ml, and 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 flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The ethyl acetate of 600ml1:1 and the mixed solution of hexamethylene and 80ml monomer solution, are passed through nitrogen 30min, are then heated to
50C°.Initiator solution 10ml is added, keeps temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid is added dropwise for 2-3 hours.System is added in remaining initiator solution, the reaction was continued 3 hours.Room temperature is reduced the temperature to, out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The above-mentioned instant macromolecule of 100g, 600ml mixed solvent cool to 5C ° or so, start that 50% hydrogen peroxide 100g is added dropwise.2-3 is small
When be added dropwise.Stop refrigeration, the reaction was continued 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:
1,8g ethyl acrylate, 3g tert-butyl acrylate, 89g third preparation of monomer solution: are added in the beaker of 500ml
Monomer solution is made with the ethyl acetate of 1:1 and the mixed solution constant volume of hexamethylene to 250ml in olefin(e) acid;
2, the preparation of initiator solution: being added the own ester of 0.4g diethyl dioxide in the beaker of 100ml, and 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 flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The ethyl acetate of 600ml1:1 and the mixed solution of hexamethylene and 80ml monomer solution, are passed through nitrogen 30min, are then heated to
50C°.Initiator solution 10ml is added, keeps temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid is added dropwise for 2-3 hours.System is added in remaining initiator solution, the reaction was continued 3 hours.Room temperature is reduced the temperature to, out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The above-mentioned instant macromolecule of 100g, 600ml mixed solvent cool to 0C ° or so, start that 50% hydrogen peroxide 80g is added dropwise.2-3 is small
When be added dropwise.Stop refrigeration, the reaction was continued 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:
1,2g lauryl methacrylate, 6g i-butyl the preparation of monomer solution: are added in the beaker of 500ml
Monomer solution is made with the ethyl acetate of 1:1 and the mixed solution constant volume of hexamethylene to 250ml in ester, 92g methacrylic acid;
2, the preparation of initiator solution: being added the own ester of 0.4g diethyl dioxide in the beaker of 100ml, and 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 flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The ethyl acetate of 600ml1:1 and the mixed solution of hexamethylene and 80ml monomer solution, are passed through nitrogen 30min, are then heated to
50C°.Initiator solution 10ml is added, keeps temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid is added dropwise for 2-3 hours.System is added in remaining initiator solution, the reaction was continued 3 hours.Room temperature is reduced the temperature to, out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The above-mentioned instant macromolecule of 100g, 600ml mixed solvent cool to 5C ° or so, start that 50% hydrogen peroxide 100g is added dropwise.2-3 is small
When be added dropwise.Stop refrigeration, the reaction was continued 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:
1,2g lauryl methacrylate, 10g styrene, 88g the preparation of monomer solution: are added in the beaker of 500ml
Monomer solution is made with the ethyl acetate of 1:1 and the mixed solution constant volume of hexamethylene to 250ml in methacrylic acid;
2, the preparation of initiator solution: being added the own ester of 0.4g diethyl dioxide in the beaker of 100ml, and 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 flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The ethyl acetate of 600ml1:1 and the mixed solution of hexamethylene and 80ml monomer solution, are passed through nitrogen 30min, are then heated to
50C°.Initiator solution 10ml is added, keeps temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid is added dropwise for 2-3 hours.System is added in remaining initiator solution, the reaction was continued 3 hours.Room temperature is reduced the temperature to, out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The above-mentioned instant macromolecule of 100g, 600ml mixed solvent cool to 10C ° or so, start that 50% hydrogen peroxide 120g is added dropwise.2-3
Hour is added dropwise.Stop refrigeration, the reaction was continued 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 isooctyl methacrylate in the beaker of 500ml, 8g butyl acrylate,
Monomer solution is made with the ethyl acetate of 1:1 and the mixed solution constant volume of hexamethylene to 250ml in 87g acrylic acid;
2, the preparation of initiator solution: being added the own ester of 0.4g diethyl dioxide in the beaker of 100ml, and 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 flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The ethyl acetate of 600ml1:1 and the mixed solution of hexamethylene and 80ml monomer solution, are passed through nitrogen 30min, are then heated to
50C°.Initiator solution 10ml is added, keeps temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid is added dropwise for 2-3 hours.System is added in remaining initiator solution, the reaction was continued 3 hours.Room temperature is reduced the temperature to, out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The above-mentioned instant macromolecule of 100g, 600ml mixed solvent cool to 5C ° or so, start that 30% hydrogen peroxide 210g is added dropwise.2-3 is small
When be added dropwise.Stop refrigeration, the reaction was continued 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:
1,2g butyl maleate, 6g dimethyl maleate, 92g the preparation of monomer solution: are added in the beaker of 500ml
Monomer solution is made with the ethyl acetate of 1:1 and the mixed solution constant volume of hexamethylene to 250ml in methacrylic acid;
2, the preparation of initiator solution: being added the own ester of 0.4g diethyl dioxide in the beaker of 100ml, and 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 flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The ethyl acetate of 600ml1:1 and the mixed solution of hexamethylene and 80ml monomer solution, are passed through nitrogen 30min, are then heated to
50C°.Initiator solution 10ml is added, keeps temperature.When occurring white precipitate in system, start remaining monomer is added dropwise molten
Liquid is added dropwise for 2-3 hours.System is added in remaining initiator solution, the reaction was continued 3 hours.Room temperature is reduced the temperature to, out
Material.75C ° of 5mmHg vacuum drying, obtains white powder.
In the 1L four-hole boiling flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The above-mentioned instant macromolecule of 100g, 600ml mixed solvent cool to 15C ° or so, start that 40% hydrogen peroxide 180g is added dropwise.2-3
Hour is added dropwise.Stop refrigeration, the reaction was continued 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 class high molecular material
Change reaction, hydrophobically modified preparation is carried out to high molecular material.Steps are as follows:
Embodiment 7
In the 1000ml three-necked flask for being furnished with mechanical agitator, water segregator, thermometer, 100g commercial polypropylene is added
Acid, 3g p-methyl benzenesulfonic acid and 8.0g laruyl alcohol, last solubilizer toluene.150 DEG C of reflux, Zhi Daofen are warming up under strong stirring
Not having water droplet to form reaction in hydrophone terminates.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 flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The above-mentioned instant macromolecule of 100g, 600ml mixed solvent cool to 5C ° or so, start that 50% hydrogen peroxide 90g is added dropwise.2-3 is small
When be added dropwise.Stop refrigeration, the reaction was continued 10 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
Embodiment 8
In the 1000ml three-necked flask for being furnished with mechanical agitator, water segregator, thermometer, 100g commercial polypropylene is added
Acid, 6g p-methyl benzenesulfonic acid and the 10.0g tert-butyl alcohol, last solubilizer benzene.110 DEG C of reflux, Zhi Daofen are warming up under strong stirring
Not having water droplet to form reaction in hydrophone terminates.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 flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The above-mentioned instant macromolecule of 100g, 600ml mixed solvent cool to 5C ° or so, start that 35% hydrogen peroxide 130g is added dropwise.2-3 is small
When be added dropwise.Stop refrigeration, the reaction was continued 10 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
Embodiment 9
In the 1000ml three-necked flask for being furnished with mechanical agitator, water segregator, thermometer, 100g commercial polypropylene is added
Acid, 3g p-methyl benzenesulfonic acid and 12.0g isobutanol, last solubilizer toluene.150 DEG C of reflux are warming up under strong stirring, until
Not having water droplet to form reaction in water segregator terminates.400 mesh filter cloth centrifugal filtrations remove solvent, 85 DEG C of vacuum drying.It obtains micro- yellowish-white
Color pulverulent solids.
In the 1L four-hole boiling flask equipped with mechanical agitator, reflux condenser, thermometer and 250ml constant pressure funnel, it is added
The above-mentioned instant macromolecule of 100g, 600ml mixed solvent cool to 5C ° or so, start that 50% hydrogen peroxide 90g is added dropwise.2-3 is small
When be added dropwise.Stop refrigeration, the reaction was continued 10 hours.Filter to obtain white powdery solids.35C ° of forced air drying.
In conclusion the present invention is described in detail by specific embodiment, but the explanation is exemplary,
Those skilled in the art can make various changes and modify on its basis, without departing from present inventive concept and spirit, this
A little change and modification should all be fallen under the scope of the present invention, and the scope of the present invention is defined by the following claims.