CN107541006A - A kind of antibacterial polyacrylonitrile butadiene styrene plastics and preparation method thereof - Google Patents
A kind of antibacterial polyacrylonitrile butadiene styrene plastics and preparation method thereof Download PDFInfo
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- CN107541006A CN107541006A CN201710722143.7A CN201710722143A CN107541006A CN 107541006 A CN107541006 A CN 107541006A CN 201710722143 A CN201710722143 A CN 201710722143A CN 107541006 A CN107541006 A CN 107541006A
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Abstract
The present invention relates to plastics antibacterial field, specifically provides a kind of method for preparing antibacterial polyacrylonitrile butadiene styrene plastics, and this method includes：(1) in the presence of aqueous solvent, poly- guanidinesalt is obtained into solids with sodium pyrithione mixing contact, the solids is dried, and crushed and obtain antiseptic；Wherein, the poly- guanidinesalt includes poly (hexamethylene) and cosmocil stearate；(2) by acrylonitrile butadiene styrene, the alternatively antiseptic, heat stabilizer progress melt blending, extruding pelletization, drying and then injection molding.The preparation method of the present invention is simple and easy, and antibiotic plastic of the invention has good antibacterial and mouldproof effect, and water resistance is strong, and application prospect is bright.
Description
Technical field
The present invention relates to a kind of antibacterial polyacrylonitrile-butadiene-styrene plastics and preparation method thereof.
Background technology
In recent years, with the raising of living standards of the people and the enhancing of health consciousness, to the need of various anti-biotic material products
Ask and be continuously increased, wherein antibacterial plastic product accounts for very big proportion, including various life products, such as has refrigerator, air-conditioning, each
Kind food containers, packaging bag, washing machine, toy product, dust catcher etc., it all employ a variety of thermoplasticity antibacterials modelings
Material, these thermoplasticity antibiotic plastics include antibacterial polypropylene (PP), antibacterial PEF (PE), antibacterial polystyrene (PS), antibacterial
Polyvinyl chloride (PVC), antibacterial polyacrylonitrile-butadiene-styrene (ABS), anti-bacteria nylon (PA), antibacterial poly terephthalic acid
Glycol ester (PET), antibacterial polyformaldehyde (POM), antibacterial polymethyl methacrylate (PMMA), antibacterial makrolon (PC)/
ABS, antibacterial PP/ABS alloys, antibacterial PA/ABS alloys etc..
At present, the document and Patents on antibiotic plastic processing are more.The preparation of antibiotic plastic, mainly passes through
A certain amount of antiseptic is added in plastic granulation process to realize.The species of antiseptic is a lot, including inorganic antiseptic,
The major class of organic antiseptic two, inorganic include Ag, Zn- zeolites, Ag, Zn- phosphate laminates, Ag, Zn- water-soluble glass etc., had
Machine class includes quaternary ammonium salts, quaternary phosphonium salt class, imidazoles, pyridines, organic metal class etc..Inorganic antiseptic and organic
Respectively there are advantage and disadvantage, inorganic heat resistance is higher, but the shortcomings that Ag series antibacterial agents are easy to change be present, and dosage is relatively large, into
This is higher；Organic antiseptic germicidal efficiency is higher, and addition is less, but poor heat resistance be present, easily separates out, and security is low etc.
Shortcoming.
Polymeric guanidine (poly- guanidine) is a kind of cation bactericidal polymer, is a kind of wide spectrum, height that the nineties occur
Effect, new type bactericide nontoxic, non-stimulated stability is good, heat decomposition temperature is higher, turn into the heat of research in sterilization field in recent years
Point.The sterilization mechanism of poly- guanidine can be construed to：Because guanidine radicals has very high activity, it is in electropositive to make polymer, is easily led to
Often adsorbed in electronegative all kinds of bacteriums, virus, so as to resist the splitting function of bacterial virus, lose bacterium, virus
Fertility, and the film of poly- guanidine formation hinders the respiration channel of microorganism, makes microorganism death by suffocation, so as to play
Good bactericidal action.
Because guanidine radicals is hydrophilic radical, therefore the water solubility of most of poly- guanidine is stronger, mainly with its aqueous solution during use
Form, the surface sterilization processing for the environment or product in the fields such as agricultural, food, hospital, food and drink；In addition, poly- guanidine is also main
For the final finishing of textile, fungus and mildew resistance function is made it have.
With the improvement of people ' s living standards with the enhancing of health consciousness, and the prevalence of multiple infectious disease in recent years, make
Requirement of the people to various anti-biotic material products is obtained to be continuously increased.Recently, research also attempts poly- guanidine being used for plastics, rubber
Deng the antibacterial application in field.For example, CN101037503A discloses a kind of production for preparing polyhexamethylene guanide propionic acid salt powder
Method, the invention utilize ion isolation exchange membrane, successfully separate polyhexamethylene guanide propionate from the aqueous solution,
Powdered samples are made, it is can be used for the Antibacterial accessory ingredient of plastics, rubber.But this polyhexamethylene guanide propionate is still
So there is certain moisture absorption, after adding in plastics or rubber, if after often soaking or often contacted with water in water,
Gradually it can be separated out after long-time from plastics or rubber, antimicrobial efficiency can reduce, or even disappear.Accordingly, it is difficult to meet
Higher antibiotic plastic or rubber are required to water resistance.
Document Synthesis and antimicrobial activity of polymeric guanidine and
(1999) 6189-6198 of biguanidine salts, Polymer 40 reports poly- six methylene for having synthesized a kind of hydrophobe
Base (double) guanidine stearate, but the antimicrobial efficiency of polyhexamethylene (double) guanidine stearic acid salt of hydrophobe is relative to water miscible
Polyhexamethylene (double) guanidine hydrochloride or polyhexamethylene (double) guanidine propionate are far short of what is expected, it usually needs in the plastic plus
Enter the double quality even more more than water-soluble poly guanidine and can be only achieved same antibacterial effect.Reason is probably on the one hand to introduce
Stearic acid root molecular weight it is more much greater than the molecular weight of the inorganic acid radicals such as salt acid group and propionate；On the other hand, stearic acid root
The antibacterial action to poly- guanidine may be weakened.In addition, after polyhexamethylene (double) guanidine stearic acid salt is added in plastics, easily
Make product yellowish, limit its application in some whites or clear plastic articles.
The content of the invention
The defects of purpose of the present invention is the antibiotic plastic poor water resistance containing poly- guanidine antiseptic for overcoming prior art, carries
Antibacterial polyacrylonitrile-butadiene-styrene plastics for a kind of water-tolerant and preparation method thereof.
To achieve these goals, the invention provides one kind to prepare antibacterial polyacrylonitrile-butadiene-styrene plastics
Method, this method includes：
(1) in the presence of aqueous solvent, poly- guanidinesalt is obtained into solids with sodium pyrithione mixing contact, by institute
Solids drying is stated, and crushes and obtains antiseptic；Wherein, the poly- guanidinesalt includes poly (hexamethylene) and polyhexamethylene
Guanoctine；
(2) by acrylic nitrile-butadiene-styrene, the antiseptic, alternatively heat stabilizer carry out melt blending, squeeze
Go out to be granulated, drying then injection molding.
In the present invention, poly (hexamethylene) does not include cosmocil stearate, and those skilled in the art know them
There are respective substance classes to cover and do not occur simultaneously mutually.
Mixed poly- guanidinesalt is used in the present invention, the poly- guanidinesalt includes poly (hexamethylene) and polyhexamethylene
Guanoctine greatly improves with the antiseptic obtained after sodium pyrithione reaction, water resistance.The present invention is prepared using simple
Technique, you can obtain the strong antibiotic plastic of water resistance, there is very high value in commercial Application.The method of the present invention is improving
While antibiotic plastic water resistance, antibacterial effect is also guaranteed.
According to the present invention, it is only necessary to the purpose of the present invention can be achieved using mixed poly- guanidinesalt, in order to further improve
The water resistance of antibiotic plastic, preferably in terms of the guanidine radicals mole total amount of poly- guanidinesalt, from the guanidine radicals of the poly (hexamethylene)
Content is 10-30%, and the guanidine radicals content from cosmocil stearate is 70-90%；More preferably with the guanidine radicals of poly- guanidinesalt
Mole total amount meter, the guanidine radicals content from the poly (hexamethylene) is 15-25%, from poly hexamethylene biguanide
The guanidine radicals content of salt is 75-85%.
According to the present invention, wherein, optional wider range of the condition of the mixing contact, further to improve water resistance,
It is preferred that the condition of the mixing contact includes：Temperature is 0-50 DEG C.
According to the present invention, wherein, according to a kind of preferred embodiment of the present invention, the mixing contact is included successively
Carry out the first mixing contact and the second mixing contacts, the temperature of the second mixing contact is lower than the temperature of the first mixing contact；It is preferred that
Low 10-40 DEG C.Using aforementioned schemes, the water resistance of antibiotic plastic can be increased substantially.
According to a kind of preferred embodiment of the present invention, the temperature of the first mixing contact is 20-40 DEG C, the second mixing
The temperature of contact is 0-10 DEG C.Thus the further raising of the water resistance of antibiotic plastic can be realized.
The method according to the invention, the time contacted to the mixing without particular/special requirement, meet reaction condition, pin
To the present invention, the time of preferably described mixing contact is 10-60min.
According to a kind of preferred embodiment of the present invention, the time of the first mixing contact is 5-15min.
According to a kind of preferred embodiment of the present invention, the time of the second mixing contact is 30-60min.
According to the present invention, the poly (hexamethylene) be this area usual definition, its substance classes covered
For the present invention, for the present invention, in order to further improve the water resistance of antibiotic plastic, preferably described polyhexamethylene guanide
Salt is polyhexamethylene guanide propionate, poly (hexamethylene) hydrochloride, polyhexamethylene guanidine nitrate and polyhexamethylene guanide carbon
One or more in hydrochlorate.
According to the present invention, the cosmocil stearate is the usual definition of this area, and the substance classes that it is covered are equal
It can be used for the present invention, for the present invention, in order to further improve the water resistance of antibiotic plastic, preferably described polyhexamethylene
Guanoctine is poly hexamethylene biguanide propionate, hexamethylene, poly hexamethylene biguanide nitrate and poly- six
One or more in di-2-ethylhexylphosphine oxide guanidine carbonate.
According to the present invention, optional wider range of the condition of the mixing contact, for the present invention, preferably pyridone
The mol ratio of thioketones sodium and guanidine radicals is 1: (0.1-4), the mol ratio of further preferred sodium pyrithione and guanidine radicals is 1:
(0.75-0.85).Under above-mentioned preferable molar ratio, can obtain antibiotic plastic water resistance and bactericidal effect one
Individual maximum balance.
According to the present invention, in contact process is mixed, preferably solid-liquid weight ratio is 1:(1-10), more preferably 1:(4-
6)。
According to the present invention, in order to further improve the water resistance of antibiotic plastic, preferably described aqueous solvent includes water and third
Ketone, wherein, more preferably with the gross weight meter of solvent, the content of water is 60-90%, and the content of acetone is 10-40%；More preferably
With the gross weight meter of solvent, the content of water is 70-80%, and the content of acetone is 20-30%.
According to the present invention, the method dried in step (1) can be common drying means, including naturally dry, baking oven
Drying, or sprayed altogether using spray drying process etc..
According to the present invention, the method crushed in step (1) can be common breaking method, to breaking method without special
It is required that.
According to the present invention, described sodium pyrithione is well known commodity, and it is generally such as United States Patent (USP)
It is by the way that 2- chloropyridine-N- oxides and NaSH and NaOH are reacted to prepare described by US3159640.Pyridone sulphur
Ketone sodium is a kind of potent water-soluble fungusproof anti-corrosion agent, has the characteristics of efficient, wide spectrum, low toxicity, stable, and it widely should
For fields such as medicine, daily use chemicals, intermetallic composite coating, agricultural product, anticorrosive paint, leather and fur products, weaving, papermaking.
According to previously described versions of the present invention, the antibiotic plastic that the present invention obtains is water-fast on the premise of bactericidal effect is ensured
Property greatly enhances.
With the method for the invention it is preferred to relative to the acrylic nitrile-butadiene-styrene of 100 parts by weight, antiseptic
0.1-20 parts by weight, heat stabilizer 0-0.5 parts by weight, nucleator 0-5 parts by weight.
The method according to the invention, optional wider range of species of heat stabilizer, heat stabilizer commonly used in the art
For the present invention, in an embodiment of the present invention, using calcium stearate as illustrating.
The method according to the invention, the equipment of melt blending can be double screw extruder, single screw extrusion machine, banburying
Machine, mill etc..The blending equipment of material mixing, various mixing equipments used in existing process technology can be used, are such as stirred
Machine, kneading machine etc..The process of mixing is without particular/special requirement.
The method according to the invention, the temperature of melt blending can be determined according to material of main part without particular/special requirement,
Consider, preferable temperature is 230 DEG C -260 DEG C.
According to the present invention, to the condition of extruding pelletization without particular/special requirement, preferably extruder temperature is 230 DEG C~260 DEG C,
Rotating speed is 300-400r.p.m.
According to the present invention, by the condition that the pellet of extrusion is dried without particular/special requirement, with reference to the conventional meanses of this area
Realize.
According to the present invention, to injecting condition without particular/special requirement, such as can be injection moulded at 220-250 DEG C of injection temperature.
In addition, in the process of antibiotic plastic, can be added with according to the needs specifically processed in material is blended
Different processing aids, such as plasticizer, reinforcing agent, fire retardant, antistatic additive, nucleator, toughener, filler, lubrication
Agent, pigment etc., its dosage are conventional amount used, or are adjusted according to the requirement of actual conditions.
The preparation method of the present invention is simple and easy, and antibiotic plastic of the invention has preferable antibacterial and mouldproof effect, and resistance to
Water-based strong, application prospect is bright.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
With reference to specific embodiment, the invention will be further described.The scope of the present invention is not by these embodiments
Limitation, the scope of the present invention propose in detail in the claims.
Prepare embodiment 1
Sodium pyrithione (scape of Hangzhou ten thousand, NPT) 77.6g (0.52mol) is added to 530g aqueous acetone solutions (acetone 20
Weight %, the weight % of water 80) in, then add polyhexamethylene guanide propionate (Shanghai is high poly-, F3000) 21.0g
(0.098mol), hexamethylene (Industrial Co., Ltd. of upper seamount, PHMB) 32g (0.146mol) are carried out
First mixing contact, the temperature of contact is 30 DEG C, time 10min；Then the second mixing contact is carried out, the temperature of contact is 5
DEG C, time 30min；Then the solid obtained after contact is dried, crushes, obtain antiseptic A1.
Prepare embodiment 2
Sodium pyrithione (scape of Hangzhou ten thousand, NPT) 64.2g (0.43mol) is added to 540g aqueous acetone solutions (acetone 25
Weight %, the weight % of water 75) in, then add polyhexamethylene guanide propionate (Shanghai is high poly-, F3000) 11.1g
(0.052mol), hexamethylene (Industrial Co., Ltd. of upper seamount, PHMB) 32g (0.146mol) carry out the
One mixing contact, the temperature of contact is 20 DEG C, time 15min；Then the second mixing contact is carried out, the temperature of contact is 10
DEG C, time 40min；Then the solid obtained after contact is dried, crushes, obtain antiseptic A2.
Prepare embodiment 3
Sodium pyrithione (scape of Hangzhou ten thousand, NPT) 64.2g (0.43mol) is added to 670g aqueous acetone solutions (acetone 30
Weight %, the weight % of water 70) in, then add polyhexamethylene guanide propionate (Shanghai is high poly-, F3000) 15.6g
(0.073mol), hexamethylene (Industrial Co., Ltd. of upper seamount,
PHMB) 32g (0.146mol) carries out the first mixing contact, and the temperature of contact is 40 DEG C, time 5min；Then
The second mixing contact is carried out, the temperature of contact is 0 DEG C, time 60min；Then the solid obtained after contact is dried,
Crush, obtain antiseptic A3.
Prepare embodiment 4
It is prepared by the method according to embodiment 3 is prepared, unlike, polyhexamethylene guanide propionate is by same molar
Poly (hexamethylene) hydrochloride (Shanghai is high poly-, F1000) replaces, and obtains antiseptic A4.
Prepare comparative example 1
It is prepared by the method according to embodiment 1 is prepared, unlike, the poly- all 0.39mol of guanidinesalt raw material poly- six methylene
Base guanidine propionate (Shanghai is high poly-, F3000), obtains antiseptic D1.
Prepare comparative example 2
It is prepared by the method according to embodiment 2 is prepared, unlike, poly- the six of the poly- all 0.172mol of guanidinesalt raw material are sub-
Methyl biguanide hydrochloride (Industrial Co., Ltd. of upper seamount, PHMB), obtains antiseptic D2.
Prepare embodiment 5
It is prepared by the method according to embodiment 1 is prepared, unlike, mixing contact directly contacts at 30 DEG C of temperature
40min, obtain antiseptic A5.
Prepare embodiment 6
It is prepared by the method according to embodiment 2 is prepared, unlike, mixing contact directly contacts at 10 DEG C of temperature
55min, obtain antiseptic A6.
Prepare embodiment 7
According to the method for preparing embodiment 3, the difference is that, the solvent acetone aqueous solution replaces with single aqueous solvent, total to use
Measure constant, obtain antiseptic A7.
Prepare embodiment 8
According to the method for preparing embodiment 3, unlike, the concentration of the solvent acetone aqueous solution is the weight % of acetone 50, water
50 weight %, total dosage is constant, obtains antiseptic A8.
Prepare embodiment 9
According to the method for preparing embodiment 3, the difference is that, total dosage of the solvent acetone aqueous solution is 1118g, is resisted
Microbial inoculum A9.
Prepare embodiment 10
According to the method for preparing embodiment 3, the difference is that, total dosage of the solvent acetone aqueous solution is 335g, obtains antibacterial
Agent A10.
Prepare embodiment 11
According to the method for preparing embodiment 3, the difference is that, the dosage of sodium pyrithione (scape of Hangzhou ten thousand, NPT) is
0.24mol, obtain antiseptic A11.
Prepare embodiment 12
According to the method for preparing embodiment 3, the difference is that, the dosage of sodium pyrithione (scape of Hangzhou ten thousand, NPT) is
0.6mol, obtain antiseptic A12.
Embodiment 1-12
Antibiotic plastic is prepared using the antiseptic A1-A12 for preparing embodiment 1-12 preparations.
Take 100 parts of ABS resin (Sinopec Gaoqiao Petrochemical Company limited company, SH-3513)；Antiseptic：0.55 part；
0.3 part of calcium stearate (Beijing Chang Yang farms chemical plant)；Passing through double screw extruder melt blending, extrusion after well mixed
Machine temperature is 230 DEG C -260 DEG C, and rotating speed is 350r.p.m melt blending extruding pelletizations, and the pellet of extrusion is dried in 90 DEG C of constant temperature
5h is dried in case, 50mm × 50mm sample M1-M12 is then molded at 220 DEG C -250 DEG C of injection temperature.
Antibacterial polyacrylonitrile-butadiene-styrene plastics M1-M12 samples boil 16 hours in 50 DEG C of water, standby；
Antibacterial polyacrylonitrile-butadiene-styrene plastics M1-M12 samples boil 50 hours in 50 DEG C of water, standby；
Antibacterial polyacrylonitrile-butadiene-styrene plastics M1-M12 samples boil 100 hours in 50 DEG C of water, standby；
Antibacterial polyacrylonitrile-butadiene-styrene plastics M1-M12 samples boil 50 hours in 60 DEG C of water, standby.
Comparative example 1-5
Use antiseptic D1, antiseptic D2, polyhexamethylene guanide propionate (Shanghai is high poly-, F3000), polyhexamethylene
Guanidine hydrochloride (Shanghai is high poly-, F1000), hexamethylene (Industrial Co., Ltd. of upper seamount, PHMB) replace
Antiseptic A1 in embodiment 1 prepares antibacterial polyacrylonitrile-butadiene-styrene N1-N5.
Antibacterial polyacrylonitrile-butadiene-styrene plastics N1-N5 samples boil 16 hours in 50 DEG C of water, standby；
Antibacterial polyacrylonitrile-butadiene-styrene plastics N1-N5 samples boil 50 hours in 50 DEG C of water, standby.
Method of testing
1st, antibacterial test standard：QB/T 2591 2003A《Antibiotic plastic Anti-microbial Performance Tests method and antibacterial effect》,
Bacterium is used in detection：Escherichia coli (Escherichia coli) ATCC 25922, Staphylococcus aureus (Staphylococcus
aureus)ATCC 6538。
2nd, antibacterial test step, tested with reference to antibiotic plastic examination criteria QB/T 2591-2003, specific steps are such as
Under：Testing sample is handled and dried with 75% ethanol disinfection, the bacteria suspension that strain is diluted to debita spissitudo with sterilized water is standby
With.Take 0.2ml bacteria suspension to drop in sample surfaces, be overlying on thereon with the thick polyethylene films (4.0cm × 4.0cm) of 0.1mm,
Bacteria suspension is set to form uniform liquid film between sample and film.Relative humidity 90% is kept to cultivate 18-24 hours at 37 DEG C.With
Sterilized water washes down bacterium solution, is diluted to appropriate concentration gradient, takes 0.1ml to be uniformly coated on the sterile letheen training prepared
Support on base.18-24 hours are cultivated in 37 DEG C, observe result.Negative control is replaced with sterilized petri dishes, and other operations are identical, is surveyed
Test result is shown in Table 1, table 2 and table 3.
The antiseptic that the method for the present invention is prepared it can be seen from data in table 1, water resistance greatly improve,
50 hours of boiling remain to keep high antibacterial activity under conditions of 50 DEG C.
Table 1
Table 2
The antiseptic obtained it can be seen from the result of table 2 under the optimum condition of the present invention, antibacterial activity are passing through
50 DEG C of high temperature boiling 100 as a child remains to keep 99.9% antibacterial activity.
Table 3
The antiseptic obtained it can be seen from the result of table 3 under the optimum condition of the present invention, antibacterial activity are passing through
60 DEG C of high temperature boiling 50 as a child remains to keep 99.9% antibacterial activity.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme,
These simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention is to various
Possible combination no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
- A kind of 1. method for preparing antibacterial polyacrylonitrile-butadiene-styrene plastics, it is characterised in that this method includes：(1) in the presence of aqueous solvent, poly- guanidinesalt is obtained into solids with sodium pyrithione mixing contact, by the solid Thing is dried, and is crushed and obtained antiseptic；Wherein, the poly- guanidinesalt includes poly (hexamethylene) and cosmocil stearate；(2) by acrylic nitrile-butadiene-styrene, the antiseptic, alternatively heat stabilizer carry out melt blending, extrusion make Grain, drying and then injection molding.
- 2. the method according to claim 11, wherein, it is sub- from described poly- six in terms of the guanidine radicals mole total amount of poly- guanidinesalt The guanidine radicals content of methyl guanidinesalt is 10-30%, and the guanidine radicals content from cosmocil stearate is 70-90%.
- 3. the method according to claim 11, wherein, it is sub- from described poly- six in terms of the guanidine radicals mole total amount of poly- guanidinesalt The guanidine radicals content of methyl guanidinesalt is 15-25%, and the guanidine radicals content from cosmocil stearate is 75-85%.
- 4. according to the method described in any one in claim 1-3, wherein, the condition of the mixing contact includes：Temperature is 0-50℃。
- 5. according to the method described in any one in claim 1-3, wherein, it is mixed that the mixing contact includes successively progress first Splice grafting touches and the second mixing contacts, and the temperature of the second mixing contact is lower than the temperature of the first mixing contact；It is preferred that low 10-40 DEG C.
- 6. according to the method for claim 5, wherein, the temperature of the first mixing contact is 20-40 DEG C, the second mixing contact Temperature is 0-10 DEG C.
- 7. according to the method described in any one in claim 1-3, wherein,The poly (hexamethylene) is polyhexamethylene guanide propionate, poly (hexamethylene) hydrochloride, polyhexamethylene guanide nitre One or more in hydrochlorate and polyhexamethylene guanidine carbonate；The cosmocil stearate is poly hexamethylene biguanide propionate, hexamethylene, poly- six methylene One or more in base biguanides nitrate and poly hexamethylene biguanide carbonate.
- 8. according to the method described in any one in claim 1-3, wherein, the condition of the mixing contact includes：The mol ratio of sodium pyrithione and guanidine radicals is 1: (0.1-4), preferably 1: (0.75-0.85)；And/orSolid-liquid weight ratio is 1:(1-10), preferably 1:(4-6)；And/orThe aqueous solvent includes water and acetone, wherein, with the gross weight meter of solvent, the content of water is 60-90%, and acetone contains Measure as 10-40%；It is preferred that the content of water is 70-80%, the content of acetone is 20-30%.
- 9. according to the method described in any one in claim 1-3, wherein,Relative to the acrylic nitrile-butadiene-styrene of 100 parts by weight, antiseptic 0.1-20 parts by weight, heat stabilizer 0-0.5 Parts by weight.
- 10. the antibacterial polyacrylonitrile that a kind of method in claim 1-9 described in any one obtains-butadiene-styrene modeling Material.
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| US3159640A (en) * | 1963-04-23 | 1964-12-01 | Olin Mathieson | Process for preparing 2-mercaptopyridine-nu oxide |
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