CN102898727A - Polypropylene master batch with functions of anti-bacteria, and mildew and algae prevention and preparation method of polypropylene master batch - Google Patents
Polypropylene master batch with functions of anti-bacteria, and mildew and algae prevention and preparation method of polypropylene master batch Download PDFInfo
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Abstract
The invention relates to a polypropylene master batch with functions of anti-bacteria, and mildew and algae prevention, and a preparation method of the polypropylene master batch. The polypropylene master batch consists of an antimicrobial agent, a mildew inhibitor, an algaecide, a coupling dispersant and a polypropylene resin. By the method provided by the invention, the antibacterial rate of the polypropylene master batch to escherichia coli and staphylococcus aureus is more than or equal to 99 percent; the level of mildew and algae prevention performance is 0 to 1, and the effects of mildew and algae prevention are durable.
Description
[technical field]
The invention belongs to technical field of polymer materials.More specifically, the present invention relates to a kind of polypropylene agglomerate with antibiotic, mildew-resistant, anti-algae function, also relate to the preparation method of described polypropylene agglomerate.
[background technology]
Nature exists the microorganisms such as various bacteriums, fungi, under water surrounding, also has a large amount of alga microbials, these microorganisms growth and breeding under suitable envrionment conditions is rapid, and some is pathogenic bacterium in these microorganisms, they can also spread disease by contact, affect the healthy of people, pollute human living environment.Therefore the product of exploitation with antibiotic, mildew-resistant, anti-algae function just seems and is necessary very much.
In present daily life, polypropylene (PP) plastics are widely used in plastic casing, wallpaper, food pack of kitchen utensils, WC Facilities, rubbish container, household electrical appliance etc.When temperature and humidity were suitable, they were very easy to be infected by bacterium.And many drinking water related products, also often be the PP goods such as water pipe, part of washing machine, water tank etc., these goods are in use easier of algae pollution, perhaps for a long time under water surrounding its product surface very easily generate mycoderm, so, bring suitable harm for the mankind and environment.
Antibiotic, mildew-resistant, anti-algae PP belong to functional plastics, it is made and usually adopts dual mode, a kind of mode is chemical modification, namely adopt chemical technology, to have the group grafting of antibiotic, mildew-resistant, anti-algae function or block in polypropylene, this method is because relate to certain chemical reaction, and complete processing is complicated, difficulty is larger, is seldom adopted by the people.The second way is physically modified, and soon antibiotic, mildew-resistant, anti-algae functional agglomerate or auxiliary agent add in the blend of plastic shaping stage, make functional product.Physically modified is easy to operate because of it, and technical difficulty is low, and suitability is wide, has become the main method of manufacturing function plastics at present.
At present, some patents or patent application also adopt physical modified method to make antibiotic PP plastics, but these antibiotic PP plastics often just have single antibacterial, do not possess the function of the anti-algae of mildew-resistant.
For example CN201110381914, denomination of invention " a kind of antibacterial polypropylene material and preparation method thereof " and CN200710074856, denomination of invention " a kind of antibacterial polypropylene material and preparation method thereof " disclose by copper-loaded zirconium phosphate antiseptic-germicide blend granulation and the method for being made antibacterial polypropylene by nanometer silver and organosilicon blend granulation.The polypropylene that these methods are produced only has antibacterial, and copper-loaded zirconium phosphate can make its product have certain color, thereby causes the application of product to be restricted, and the anti-microbial property of copper class antiseptic-germicide is also than a little less than the silver system.
CN200610147549, denomination of invention " high-effectively antibiotic polypropylene master batch and preparation method thereof " disclose to adopt carries silver-colored hydroxyl zirconium sodium phosphate or glass carrying silver antimicrobials, makes the polypropylene antibacterial master batch by the mode of mixing granulation.The master batch that this invention is made only has antibacterial, does not possess simultaneously the function of mildew-resistant, anti-algae.
CN03139107 and CN96106368 also disclose respectively and adopted silver is antibacterial matrices and the antibacterial matrices that adopts zeolite, silicon-dioxide, absorption ammonium salt to prepare, further make the technology of antibiotic PP, these different preparation methods only provide single antibacterial for polypropylene.
CN00127954, denomination of invention " method for making and the sky of antibacterial antimildew polyacrylic fibres fall filtering net " disclose the method that the absorption nanometer silver is made antibacterial antimildew polyacrylic in the silicate clay micropore that adopts, studies show that nanometer silver has excellent anti-microbial property, provide excellent fungicidal properties but use single nanometer silver to be difficult to material.
The inventor is on the basis of summing up prior art, by experimental study is a large amount of for many years, filter out optimization of C/C composites, give the good germ resistance of PP material, mildew resistance, anti-algae property, and adopting on unique powder handling technique improves a lot the processing characteristics of product, by art breading, various compositions compatibility in resin is good, and dispersing property is excellent.The present invention not only technique is simple, and product performance are very excellent.
[summary of the invention]
[technical problem that will solve]
The purpose of this invention is to provide a kind of polypropylene agglomerate with antibiotic, mildew-resistant and anti-algae function.
Another object of the present invention provides the preparation method of described polypropylene agglomerate.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of polypropylene agglomerate with antibiotic, mildew-resistant and anti-algae function.
Described polypropylene agglomerate is comprised of by weight following component:
1～20 part of antiseptic-germicide;
1～20 part of mould inhibitor;
1～20 part of algaecide;
0.3～1 part of coupling dispersion agent;
75～90 parts of acrylic resins;
Described antiseptic-germicide is silver-colored zinc antiseptic-germicide;
Described mould inhibitor is nitrile mould inhibitor, imidazoles mould inhibitor or organic salt mould inhibitor;
Described algaecide is the isothiazolinone algaecide;
Described coupling dispersion agent is one or more coupling dispersion agents that are selected from silane series coupling dispersion agent, Aluminate series coupling dispersion agent or titanic acid ester series coupling dispersion agent.
A preferred embodiment of the invention, described polypropylene agglomerate is comprised of by weight following component:
5～14 parts of antiseptic-germicides;
5～14 parts of mould inhibitors;
5～14 parts of algaecides;
0.4～0.8 part of coupling dispersion agent;
78～85 parts of acrylic resins.
According to another kind of preferred implementation of the present invention, described silver-colored zinc antiseptic-germicide is that zeolite carries silver-colored zinc antiseptic-germicide, glass carrying silver antimicrobials or zirconium phosphate carrying silver antimicrobials.
According to another kind of preferred implementation of the present invention, described nitrile mould inhibitor is termil or 4-chloro-styrene base nitrile; Described imidazoles mould inhibitor is the N-(2-benzimidazolyl-)-Urethylane, 2-(thiazole-4-yl) benzoglyoxaline or 1-(n-butylamine-based formyl)-the 2-benzimidazole carbamate; Described organic salt mould inhibitor is copper 8-quinolinolate or N-N ' ziram.
According to another kind of preferred implementation of the present invention, described isothiazolinone algaecide is MIT, CMIT or 4,5-, two chloro-Kathons.
According to another kind of preferred implementation of the present invention, described silane series coupling dispersion agent is the compound with following general formula (1):
Y(CH
2)
nSiX
3………（1）
In the formula:
n=0~3
Y is selected from methyl, vinyl, amino, epoxy group(ing), sulfydryl or acryloyl-oxy propyl group;
X is selected from alkoxyl group, aryloxy, acyl group or chloro;
Described Aluminate series coupling dispersion agent is selected from SG-Al821, DL-411, DL-411AF, DL-411D, DL-411DF or anti-settling Aluminate ASA;
Described titanic acid ester series coupling dispersion agent is the compound with following general formula (2):
ROO
(4-n)Ti(OX-R'Y)
n………（2）
In the formula:
RO-is a kind of hydrolyzable (C
1-C
4) alkoxy-functional;
It is carboxyl, alkoxyl group, sulfonic group, phosphorus base group that OX-is selected from;
R' is 3-5 carbon skeleton (CH
2)-Ji;
Y is the reactive group of thermosetting polymer;
N=2 or 3;
According to another kind of preferred implementation of the present invention, described acrylic resin is that melting index is the polypropylene of 5-40g/10min.
According to another kind of preferred implementation of the present invention, described polypropylene agglomerate is to the antibiotic rate of intestinal bacteria and streptococcus aureus 〉=99%; Fungicidal properties and anti-algae performance are 0～1 grade.
The invention still further relates to the preparation method of described polypropylene agglomerate.
This preparation method's step is as follows:
A, surface treatment and mix
The described coupling dispersion agent of the described antiseptic-germicide of 1～20 weight part and 0.3～1 weight part was processed under the condition of rotating speed 500～600rpm 3～5 minutes in high-speed mixer, obtained a kind of antibiotic mixture; Then
Described antibiotic mixture was mixed under the condition of rotating speed 500～600rpm 3～5 minutes in high-speed mixer with the described mould inhibitor of 1～20 weight part and the described algaecide of 1～20 weight part, then toward wherein adding 75～90 weight part profax resin granular materials, continuation mixed under the condition of rotating speed 500～600rpm 3～5 minutes in high-speed mixer, obtained a kind of mixture;
B, melting mixing: the mixture that allows step A obtain melt extrudes by twin screw extruder, obtains described polypropylene agglomerate with antibiotic, mildew-resistant and anti-algae function.
A preferred embodiment of the invention, described to melt extrude be to carry out under the condition of 180～200 ℃ of Heating temperatures, engine speed 200-230 rev/min and feeding 18-24Hz.
The below will describe technical scheme of the present invention in more detail.
The present invention relates to a kind of polypropylene agglomerate with antibiotic, mildew-resistant and anti-algae function.
Described polypropylene agglomerate is comprised of by weight following component:
1～20 part of antiseptic-germicide;
1～20 part of mould inhibitor;
1～20 part of algaecide;
0.3～1 part of coupling dispersion agent;
75～90 parts of acrylic resins;
Described antiseptic-germicide is silver-colored zinc antiseptic-germicide.
Described silver-colored zinc antiseptic-germicide is that zeolite carries silver-colored zinc antiseptic-germicide, glass carrying silver antimicrobials or zirconium phosphate carrying silver antimicrobials.
In the present invention, to carry the zeolite that uses in the silver-colored zinc antiseptic-germicide be that 4A zeolite, silver content are that 0.2～0.45 % by weight, zinc content are 1～4 % by weight to described zeolite.Different silver-colored zinc content not only affect the anti-microbial property of its product, but also affect the discoloration of its product.Preferably, described silver content is that 0.2 % by weight, described zinc content are 4 % by weight.It is that our company (Beijing Chonygao Nano Science and Technology Co., Ltd) trade mark is the product of AMZ that the zeolite that the present invention uses carries silver-colored zinc antiseptic-germicide.
Described zirconium phosphate carrying silver antimicrobials is that a kind of bedded zirconium phosphate carries silver products, and wherein silver content is 1～3 % by weight.The different silver contents that this bedded zirconium phosphate carries silver products can affect anti-microbial property and the discoloration of its product.Preferably, described silver content is 2.8 % by weight.The used zirconium phosphate carrying silver antimicrobials of the present invention can be that our company (Beijing Chonygao Nano Science and Technology Co., Ltd) trade mark is product or profit river, the Shanghai nanometer company product sold of AMR.
The silver content of described glass carrying silver antimicrobials is 1～3 % by weight, and wherein the silver content size determines anti-microbial property and the discoloration of its product.Preferably, described silver content is 2.8 % by weight, and the used glass carrying silver antimicrobials of the present invention is Japanese stoneman nitre Subsidiary Company or Japanese emerging nitrous Subsidiary Company product sold.
In the present invention, described mould inhibitor should be appreciated that it is mould to be had kill or restraining effect, prevents the preparation that application goes mouldy.
In the present invention, described mould inhibitor is nitrile mould inhibitor, imidazoles mould inhibitor or organic salt mould inhibitor.
Described nitrile mould inhibitor is termil or 4-chloro-styrene base nitrile; The molecular formula of termil is C
8Cl
4N
2, CAS 1897-45-6, the present invention preferably uses Wuhan gold promise chemical industry company limited and Shandong to like general chemical company limited product sold.4-chloro-styrene base nitrile molecular formula is C
9ClH
7N, CAS 1885-38-7, the present invention preferably uses the product of Guangzhou one hundred silent bio tech ltd.
Described imidazoles mould inhibitor is the N-(2-benzimidazolyl-)-Urethylane, 2-(thiazole-4-yl) benzoglyoxaline or 1-(n-butylamine-based formyl)-the 2-benzimidazole carbamate.N-(2-benzimidazolyl-for example)-molecular formula of Urethylane is C
9H
9N
3O
2, CAS 10605-21-7, the present invention uses Hubei Xin Dali company limited and Tianjin Skien to think biochemical technology company limited product sold.The 2-(thiazole-4-yl) molecular formula of benzoglyoxaline is C
10H
7N
3S, CAS 148-79-8, the present invention preferably uses the product of the biochemical company limited of Hubei Xin Dali.1-(n-butylamine-based formyl)-2-benzimidazole carbamate molecular formula is C
14H
18N
4O
3, CAS 17804-35-2, the present invention preferably uses the product of Nanjing benevolence letter chemical industry company limited and Jiangyin insecticide factory of Jiangsu Yong Lian group.
Described organic salt mould inhibitor is copper 8-quinolinolate or N-N ' ziram.The molecular formula of copper 8-quinolinolate is C
18H
12N
2O
2Cu, CAS 10380-28-6, the present invention preferably adopts Hubei Chu Sheng waffle worker company limited and Shanghai Mai Ruier chemical technology company limited product sold.The molecular formula of N-N ' ziram is C
6H
12N
2S
4Zn, CAS 137-30-4, the present invention preferably uses the product of Shandong Wan Duofu chemistry company limited.
In the present invention, described algaecide should be appreciated that it is to have a broad-spectrum bactericidal capacity, effectively the permeation cell wall, decompose cell DNA, thereby kill and suppress the preparation of its algae reproduction.
Described algaecide is the isothiazolinone algaecide.Described isothiazolinone algaecide for example is MIT, CAS No2682-20-4, CMIT, CAS No.26172-55-4; They preferably use the former Fine Chemical Co., Ltd of Dalian star and granary Pu Yuan chemical industry company limited product sold; 4,5-, two chloro-Kathons (DCOIT), CAS 64359-81-5 preferably uses Dalian Bio-Chem Co., Ltd. and Wuhan Ford Fine Chemical Co., Ltd product sold.
In the present invention, described coupling dispersion agent is one or more coupling dispersion agents that are selected from silane series coupling dispersion agent, Aluminate series coupling dispersion agent or titanic acid ester series coupling dispersion agent.
Described silane series coupling dispersion agent is the compound with following general formula (1):
Y(CH
2)
nSiX
3………（1）
In the formula:
n=0~3
Y is organo-functional group non-hydrolysis, that can be combined with high molecular polymer, for example is selected from the organo-functional group of methyl, vinyl, amino, epoxy group(ing), sulfydryl or acryloyl-oxy propyl group;
X is hydrolysable group, for example is selected from alkoxyl group, aryloxy, acyl group or chloro group.
Described silane series coupling dispersion agent preferably X is the compound of methoxyl group and oxyethyl group, γ-aminopropyl triethoxysilane (CAS 919-30-2 for example, EINECS 213-048-4), vinyltriethoxysilane (CAS 78-08-0), N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane (CAS73069-29-2), they are the product that can buy acquisition on market.
Described Aluminate series coupling dispersion agent can be SG-Al821 (distearyl acyl-oxygen sec.-propyl Aluminate), DL-411, DL-411AF, DL-411D, DL-411DF or anti-settling Aluminate ASA, wherein ASA contain can with the group of active hydrogen reaction, thereby can with the mineral filler generation bonding action of hydroxyl, carboxyl or surface adsorption water, improve affinity and the bonding force of mineral filler and organic polymer, thereby the generation result of prevention can also improve bonding strength.The said products is from the market obtainable product, for example the coupling dispersion agent DL-411 series product of Foochow novel meticulous Materials Co., Ltd of section of unit sale.
Described titanic acid ester series coupling dispersion agent is the compound with following general formula (2):
ROO
(4-n)Ti(OX-R'Y)
n………（2）
In the formula:
RO-is a kind of hydrolyzable (C
1-C
4) alkoxy-functional;
It is carboxyl, alkoxyl group, sulfonic group, phosphorus base group that OX-is selected from;
R' is 3-5 carbon skeleton (CH
2)-Ji;
Y is the reactive group of thermosetting polymer;
N=2 or 3.
RO-can react with the inorganics surface hydroxyl, thereby reaches the purpose of chemical coupling.
Preferably, described titanic acid ester series coupling dispersion agent is sec.-propyl three stearic acid titanic acid ester (CAS61417-49-0), tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanic acid ester, (CAS65460-52-8) or sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester (CAS67691-13-8), they are from the market obtainable product.
In the present invention, described acrylic resin is the polypropylene of melting index 5-40g/10min, the acrylic resin of productions such as Yanshan Petrochemical company or Qilu Petrochemical.
According to the present invention, if acrylic resin is 78～85 weight parts, the amount of its antiseptic-germicide is during less than 1 weight part, then polypropylene agglomerate anti-microbial property of the present invention can be a little less than; The amount of its antiseptic-germicide is during greater than 20 weight part, and then the anti-algae performance of the mildew-resistant of polypropylene agglomerate of the present invention can be adversely affected, and therefore, the amount of its antiseptic-germicide is that 1～20 weight part is suitable, is preferably 5～14 weight parts, more preferably 8～10 weight parts.
If acrylic resin is 78～85 weight parts, the amount of its mould inhibitor is during less than 1 weight part, and then polypropylene agglomerate fungicidal properties of the present invention can not ensure; The amount of its mould inhibitor is during greater than 20 weight part, and then the anti-microbial property of polypropylene agglomerate and anti-algae performance can be adversely affected, and therefore, the amount of its mould inhibitor is that 1～20 weight part is suitable, is preferably 5～14 weight parts, more preferably 8～10 weight parts.
Similarly, if acrylic resin is 78～85 weight parts, the amount of its algaecide is during less than 1 weight part, and then the anti-algae performance of polypropylene agglomerate can be poor; The amount of its algaecide is during greater than 20 weight part, and then the antibacterial and mouldproof performance of polypropylene agglomerate of the present invention can be adversely affected, and therefore, the amount of its algaecide is that 1～20 weight part is suitable, is preferably 5～14 weight parts, more preferably 8～10 weight parts.
If acrylic resin is 78～85 weight parts, the amount of its coupling dispersion agent is during less than 0.3 weight part, and then polypropylene agglomerate of the present invention can produce and disperse inhomogeneous problem; The amount of its coupling dispersion agent is during greater than 1 weight part, then polypropylene agglomerate is processed into that outward appearance and the mechanical property of goods can be subject to bad impact behind the goods, therefore, the amount of its coupling dispersion agent is that 0.3～1 weight part is suitable, be preferably 0.4～0.8 weight part, more preferably 0.4～0.6 weight part.
The below has carried out antibiotic, mildew-resistant and anti-algae performance test to polypropylene agglomerate of the present invention.
A, carried out the test of anti-microbial property according to QB/T2591-2003 " antibiotic plastic anti-microbial property test method and antibacterial effect " standard, the results are shown in Table 1 for it.
Table 1: the antibacterial tests result of polypropylene agglomerate of the present invention
The test-results of table 1 most clearly shows, polypropylene agglomerate of the present invention has very excellent anti-microbial property.
B, carried out the fungicidal properties test according to QB/T2591-2003 " antibiotic plastic anti-microbial property test method and antibacterial effect " standard, the results are shown in Table 2 for it.
Table 2: the mold test result of polypropylene agglomerate of the present invention
According to the fungicidal properties index of QB/T2591-2003 standard code, can be thought by table 2 test-results, polypropylene agglomerate of the present invention has very excellent fungicidal properties.
C, carried out the test of anti-fungi performance according to GB/T 24127-2009 " plastics anti-algae performance experimental technique ", the results are shown in Table 3 for it.
Table 3: the anti-algae test-results of polypropylene agglomerate of the present invention
According to the anti-algae performance index of GB/T 24127-2009 standard code, can be thought by the test-results of table 3, polypropylene agglomerate of the present invention has very excellent anti-algae performance.
This shows, polypropylene agglomerate of the present invention is to the antibiotic rate of intestinal bacteria and streptococcus aureus 〉=99%; Its fungicidal properties and anti-algae performance are 0～1 grade.
The invention still further relates to the preparation method of described polypropylene agglomerate.
This preparation method's step is as follows:
A, surface treatment and mix
The described coupling dispersion agent of the described antiseptic-germicide of 1～20 weight part and 0.3～1 weight part was processed under the condition of rotating speed 500～600rpm 3～5 minutes in high-speed mixer, obtained a kind of antibiotic mixture.
Described silver-colored zinc antiseptic-germicide is silver-colored zinc antiseptic-germicide;
Described coupling dispersion agent is one or more coupling dispersion agents that are selected from silane series coupling dispersion agent, Aluminate series coupling dispersion agent or titanic acid ester series coupling dispersion agent.
The details of described silver-colored zinc antiseptic-germicide and described coupling dispersion agent does not repeat them here as previously described.
In this step, these materials condition lower surface in the 500-600rpm rotating speed in high-speed mixer was processed 3-5 minute, and this time can guarantee that its material surface treatment is more abundant; If the treatment time is less than 3 minutes, then the material surface treatment is insufficient; If grume more than 5 minutes, then may because of the material frictional heat, occur and reunite, thereby cause treatment effect not good in the treatment time.
Then, described antibiotic mixture was mixed under the condition of rotating speed 500～600rpm 3～5 minutes in high-speed mixer with the described mould inhibitor of 1～20 weight part and the described algaecide of 1～20 weight part, then toward wherein adding 75～90 weight part profax resin granular materials, continuation mixed under the condition of rotating speed 500～600rpm 3～5 minutes in high-speed mixer, obtained a kind of mixture.
Described mould inhibitor is nitrile mould inhibitor, imidazoles mould inhibitor or organic salt mould inhibitor.
Described algaecide is the isothiazolinone algaecide.
Described acrylic resin is that melting index is the polypropylene of 5-40g/10min.
The details of described mould inhibitor, algaecide and acrylic resin does not repeat them here as previously described.
In this step, described antibiotic mixture, mould inhibitor, algaecide and profax resin granular material were processed 3-5 minute under the condition of 500-600rpm rotating speed in high-speed mixer, and this time can guarantee that its mixing of materials is more even; If the treatment time is less than 3 minutes, then mixing of materials is inhomogeneous; If the treatment time more than 5 minutes, then may grume occur reunite, thereby cause material inhomogeneous because of the material frictional heat, affect production technique and quality product.
B, melting mixing: the mixture that allows step A obtain melt extrudes by twin screw extruder, obtains described polypropylene agglomerate with antibiotic, mildew-resistant and anti-algae function.
It is described that to melt extrude be to carry out under the condition of 180～200 ℃ of Heating temperatures, engine speed 200-230 rev/min and feeding 18-24Hz.
Described twin screw extruder is product sold in the market, for example the TE-65 type parallel dual-screw extruding machine produced of the inferior chemical equipment in sets of Nanjing section company limited.
Adopt the anti-algae polypropylene agglomerate of antibacterial and mouldproof of the inventive method preparation, it is antibiotic, mildew-resistant, anti-algae excellent performance, and its functional effect is lasting.The most important thing is, inorganic antiseptic superfine powder of the present invention is in use through coating and surface treatment, and is good with matrix acrylic resin compatibility, and dispersing property is also fine in resin.
[beneficial effect]
The invention has the beneficial effects as follows: adopt the anti-algae polypropylene agglomerate of antibacterial and mouldproof of the inventive method preparation, to the antibiotic rate of intestinal bacteria and streptococcus aureus 〉=99%; Its fungicidal properties and anti-algae performance are 0～1 grade.Inorganic antiseptic superfine powder of the present invention is in use through coating and surface treatment, and is good with matrix acrylic resin compatibility, and dispersing property is also fine in resin.
[embodiment]
Can understand better the present invention by following embodiment.
Embodiment 1: the preparation of polypropylene agglomerate of the present invention
This embodiment implementation step is as follows:
A, surface treatment and mix
The described zirconium phosphate carrying silver antimicrobials of 5 weight parts and 0.3 parts by weight of ethylene ethyl triethoxy silicane alkane coupling dispersion agent, create good mechanical company limited in the Zhangjagang City and produce in the SHR-10A type high-speed mixer and under the condition of rotating speed 500rpm, processed 3 minutes, obtain a kind of antibiotic mixture;
Then
The MIT algaecide that the termil mould inhibitor that described antibiotic mixture and 1 weight part Wuhan gold promise chemical industry company limited produce and the former Fine Chemical Co., Ltd of 5 weight part Dalian stars produce is in its high-speed mixer, under the condition of rotating speed 500rpm, mixed 3 minutes, then toward the profax resin granular material that wherein adds 75 weight part melting index 5g/10min, continuation mixed 4 minutes under the condition of rotating speed 500rpm in this high-speed mixer, obtained a kind of mixture;
B, melting mixing: the TE-65 type parallel dual-screw extruding machine that the mixture that allows step A obtain is produced by inferior chemical equipment in sets company limited of Nanjing section, under the condition of 200 rev/mins of 180 ℃ of Heating temperatures, engine speed and feeding 18Hz, melt extrude, obtain described polypropylene agglomerate with antibiotic, mildew-resistant and anti-algae function.
Adopt the testing method of describing in the present specification, tested the polypropylene agglomerate of the present embodiment preparation to antibiotic rate, its fungicidal properties and the anti-algae performance of intestinal bacteria and streptococcus aureus, its measurement result is listed among the table 4-6.
Embodiment 2: the preparation of polypropylene agglomerate of the present invention
This embodiment implementation step is as follows:
A, surface treatment and mix
The described zeolite of 1 weight part carries the compound coupling dispersion agent of sec.-propyl distearyl acid titanic acid ester of silver-colored zinc antiseptic-germicide and 1 weight part, create good mechanical company limited in the Zhangjagang City and produce in the SHR-10A type high-speed mixer and under the condition of rotating speed 600rpm, processed 5 minutes, obtain a kind of antibiotic mixture; Then
The N-(2-benzimidazolyl base that described antibiotic mixture and 15 weight part Hubei Xin Dali company limiteds produce)-CMIT algaecide that Urethylane mould inhibitor and 15 weight part granary Pu Yuan chemical industry company limiteds produce is in its high-speed mixer, under the condition of rotating speed 600rpm, mixed 5 minutes, then toward the profax resin granular material that wherein adds 90 weight part melting index 40g/10min, continuation mixed 5 minutes under the condition of rotating speed 600rpm in this high-speed mixer, obtained a kind of mixture;
B, melting mixing: the TE-65 type parallel dual-screw extruding machine that the mixture that allows step A obtain is produced by inferior chemical equipment in sets company limited of Nanjing section, under the condition of 230 rev/mins of 200 ℃ of Heating temperatures, engine speed and feeding 24Hz, melt extrude, obtain described polypropylene agglomerate with antibiotic, mildew-resistant and anti-algae function.
Adopt the testing method of describing in the present specification, tested the polypropylene agglomerate of the present embodiment preparation to antibiotic rate, its fungicidal properties and the anti-algae performance of intestinal bacteria and streptococcus aureus, its measurement result is listed among the table 4-6.
Embodiment 3: the preparation of polypropylene agglomerate of the present invention
This embodiment implementation step is as follows:
A, surface treatment and mix
The described glass carrying silver antimicrobials of 20 weight parts and 0.5 weight part distearyl acyl-oxygen sec.-propyl Aluminate coupling dispersion agent, create good mechanical company limited in the Zhangjagang City and produce in the SHR-10A type high-speed mixer and under the condition of rotating speed 520rpm, processed 4 minutes, obtain a kind of antibiotic mixture; Then
4 of the copper 8-quinolinolate mould inhibitor that described antibiotic mixture and 20 weight part Shanghai Mai Ruier chemical technology company limiteds produce and the production of 1 weight part Dalian Bio-Chem Co., Ltd., 5-two chloro-Kathon algaecides are in its high-speed mixer, under the condition of rotating speed 520rpm, mixed 5 minutes, then toward the profax resin granular material that wherein adds 80 weight part melting index 30g/10min, continuation mixed 3 minutes under the condition of rotating speed 520rpm in this high-speed mixer, obtained a kind of mixture;
B, melting mixing: the TE-65 type parallel dual-screw extruding machine that the mixture that allows step A obtain is produced by inferior chemical equipment in sets company limited of Nanjing section, under the condition of 210 rev/mins of 190 ℃ of Heating temperatures, engine speed and feeding 20Hz, melt extrude, obtain described polypropylene agglomerate with antibiotic, mildew-resistant and anti-algae function.
Adopt the testing method of describing in the present specification, tested the polypropylene agglomerate of the present embodiment preparation to antibiotic rate, its fungicidal properties and the anti-algae performance of intestinal bacteria and streptococcus aureus, its measurement result is listed among the table 4-6.
Embodiment 4: the preparation of polypropylene agglomerate of the present invention
This embodiment implementation step is as follows:
A, surface treatment and mix
The described zirconium phosphate carrying silver antimicrobials of 15 weight parts and 0.8 parts by weight of ethylene ethyl triethoxy silicane alkane coupling dispersion agent are created good mechanical company limited and are produced in the SHR-10A type high-speed mixer in the Zhangjagang City, under the condition of rotating speed 580rpm, processed 5 minutes, obtain a kind of antibiotic mixture; Then
The MIT algaecide that the termil mould inhibitor that described antibiotic mixture and 5 weight part Wuhan gold promise chemical industry company limited produce and the former Fine Chemical Co., Ltd of 20 weight part Dalian stars produce is in its high-speed mixer, under the condition of rotating speed 580rpm, mixed 4 minutes, then toward the profax resin granular material that wherein adds 85 weight part melting index 15g/10min, continuation mixed 5 minutes under the condition of rotating speed 580rpm in this high-speed mixer, obtained a kind of mixture;
B, melting mixing: the TE-65 type parallel dual-screw extruding machine that the mixture that allows step A obtain is produced by inferior chemical equipment in sets company limited of Nanjing section, under the condition of 220 rev/mins of 185 ℃ of Heating temperatures, engine speed and feeding 22Hz, melt extrude, obtain described polypropylene agglomerate with antibiotic, mildew-resistant and anti-algae function.
Adopt the testing method of describing in the present specification, tested the polypropylene agglomerate of the present embodiment preparation to antibiotic rate, its fungicidal properties and the anti-algae performance of intestinal bacteria and streptococcus aureus, its measurement result is listed among the table 4-6.
According to QB/T2591-2003 " antibiotic plastic anti-microbial property test method and antibacterial effect " standard testing the polypropylene agglomerate of embodiment 1-4 preparation to the antibiotic rate of intestinal bacteria and streptococcus aureus, the results are shown in Table 4 for it.
Table 4: embodiment 1-4 prepares the antibacterial tests result of polypropylene agglomerate
According to QB/T2591-2003 " antibiotic plastic anti-microbial property test method and antibacterial effect " standard testing the fungicidal properties of polypropylene agglomerate of embodiment 1-4 preparation, the results are shown in Table 5 for it.
Table 5: embodiment 1-4 prepares the mold test result of polypropylene agglomerate
Tested the anti-algae performance of the polypropylene agglomerate of embodiment 1-4 preparation according to GB/T 24127-2009 " plastics anti-algae performance experimental technique ", the results are shown in Table 6 for it.
Table 6: embodiment 1-4 prepares the anti-algae performance test results of polypropylene agglomerate
The test-results listed of table 4-6 clearly illustrates that, polypropylene agglomerate of the present invention has very excellent antibiotic, mildew-resistant and anti-algae function.
Claims (10)
1. polypropylene agglomerate with antibiotic, mildew-resistant and anti-algae function is characterized in that what described polypropylene agglomerate was comprised of by weight following component:
1～20 part of antiseptic-germicide;
1～20 part of mould inhibitor;
1～20 part of algaecide;
0.3～1 part of coupling dispersion agent;
75～90 parts of acrylic resins;
Described antiseptic-germicide is silver-colored zinc antiseptic-germicide;
Described mould inhibitor is nitrile mould inhibitor, imidazoles mould inhibitor or organic salt mould inhibitor;
Described algaecide is the isothiazolinone algaecide;
Described coupling dispersion agent is one or more coupling dispersion agents that are selected from silane series coupling dispersion agent, Aluminate series coupling dispersion agent or titanic acid ester series coupling dispersion agent.
2. polypropylene agglomerate according to claim 1 is characterized in that what described polypropylene agglomerate was comprised of by weight following component:
5～14 parts of antiseptic-germicides;
5～14 parts of mould inhibitors;
5～14 parts of algaecides;
0.4～0.8 part of coupling dispersion agent;
78～85 parts of acrylic resins.
3. polypropylene agglomerate according to claim 1 is characterized in that described silver-colored zinc antiseptic-germicide is that zeolite carries silver-colored zinc antiseptic-germicide, glass carrying silver antimicrobials or zirconium phosphate carrying silver antimicrobials.
4. polypropylene agglomerate according to claim 1 is characterized in that described nitrile mould inhibitor is termil or 4-chloro-styrene base nitrile; Described imidazoles mould inhibitor is the N-(2-benzimidazolyl-)-Urethylane, 2-(thiazole-4-yl) benzoglyoxaline or 1-(n-butylamine-based formyl)-the 2-benzimidazole carbamate; Described organic salt mould inhibitor is copper 8-quinolinolate or N-N ' ziram.
5. polypropylene agglomerate according to claim 1 is characterized in that described isothiazolinone algaecide is MIT, CMIT or 4,5-, two chloro-Kathons.
6. polypropylene agglomerate according to claim 1 is characterized in that described silane series coupling dispersion agent is the compound with following general formula (1):
Y(CH
2)
nSiX
3………（1）
In the formula:
n=0~3
Y is selected from methyl, vinyl, amino, epoxy group(ing), sulfydryl or acryloyl-oxy propyl group;
X is selected from alkoxyl group, aryloxy, acyl group or chloro;
Described Aluminate series coupling dispersion agent is selected from SG-Al821, DL-411, DL-411AF, DL-411D, DL-411DF or anti-settling Aluminate ASA;
Described titanic acid ester series coupling dispersion agent is the compound with following general formula (2):
ROO
(4-n)Ti(OX-R'Y)
n………（2）
In the formula:
RO-is a kind of hydrolyzable (C
1-C
4) alkoxy-functional;
It is carboxyl, alkoxyl group, sulfonic group, phosphorus base group that OX-is selected from;
R' is 3-5 carbon skeleton (CH
2)-Ji;
Y is the reactive group of thermosetting polymer;
N=2 or 3.
7. polypropylene agglomerate according to claim 1 is characterized in that described acrylic resin is that melting index is the polypropylene of 5-40g/10min.
8. the described polypropylene agglomerate of each claim according to claim 1-7 is characterized in that described polypropylene agglomerate is to the antibiotic rate of intestinal bacteria and streptococcus aureus 〉=99%; Fungicidal properties and anti-algae performance are 0～1 grade.
9. the preparation method of the described polypropylene agglomerate of each claim according to claim 1-8 is characterized in that the step of the method is as follows:
A, surface treatment and mix
The described coupling dispersion agent of the described antiseptic-germicide of 1～20 weight part and 0.3～1 weight part was processed under the condition of rotating speed 500～600rpm 3～5 minutes in high-speed mixer, obtained a kind of antibiotic mixture; Then
Described antibiotic mixture was mixed under the condition of rotating speed 500～600rpm 3～5 minutes in high-speed mixer with the described mould inhibitor of 1～20 weight part and the described algaecide of 1～20 weight part, then toward wherein adding 75～90 weight part profax resin granular materials, continuation mixed under the condition of rotating speed 500～600rpm 3～5 minutes in high-speed mixer, obtained a kind of mixture;
B, melting mixing: the mixture that allows step A obtain melt extrudes by twin screw extruder, obtains described polypropylene agglomerate with antibiotic, mildew-resistant and anti-algae function.
10. preparation method according to claim 9 is characterized in that described to melt extrude be to carry out under the condition of 180～200 ℃ of Heating temperatures, engine speed 200-230 rev/min and feeding 18-24Hz.
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