CN106633384A - Scratch-resistant anti-microbial high-performance anti-flaming PP composite material and preparation method thereof - Google Patents
Scratch-resistant anti-microbial high-performance anti-flaming PP composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a scratch-resistant anti-microbial high-performance anti-flaming PP composite material and a preparation method thereof. The scratch-resistant anti-microbial high-performance anti-flaming PP composite material is formed by the following components by weight: 40-60 parts of PP, 30-50 parts of modified nano aluminium hydroxide, 8-12 parts of an anti-microbial agent, 0.1-0.5 parts of antioxygen, and 0.4-0.8 parts of a lubricant. The technical solution is capable of grafting PMMA on the nano aluminium hydroxide, forming a coating layer on the surface of the nano aluminium hydroxide, reducing the surface energy of the nano aluminium hydroxide particle, dispersing the nano aluminium hydroxide in the PP matrix well, preventing the agglomeration of the nano aluminium hydroxide, and improving the fire resistance and the physical performance of the PP composite material.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly relates to a kind of scratch-resistant antibacterial high-performance refractory PP composite woods
Material and preparation method thereof.
Background technology
With the development of modern science and technology, requirement more and more higher of the people to material property, especially to general-purpose plastics polypropylene
(PP) material.PP is mainly used in the fields such as automobile, household electrical appliances, tubing, medical treatment, food, but because the wearability of PP materials is poor, resistance
Combustion poor performance, anti-microbial property are bad, and these shortcomings greatly limit application of the PP composites on some special dimensions.
Polymethyl methacrylate (PMMA) is grafted into nano-aluminum hydroxide, then uses its modified polypropene, obtained PP
Not only wearability, fire resistance, anti-microbial property are improved, and physical property was relatively also improved originally, and the method is so far
Not yet see report.
The content of the invention
It is an object of the invention to provide a kind of scratch-resistant antibacterial high-performance refractory PP composites and preparation method thereof, to carry
The wearability of high PP composites, anti-flammability and other physical properties.
The present invention is achieved by the following technical solutions：
A kind of scratch-resistant antibacterial high-performance refractory PP composites, are made up of the component of following weight portion：
The preparation method of the modified aluminum trihydroxide, comprises the following steps：
1) a certain amount of methyl methacrylate, nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride and dodecyl are weighed
Benzene sulfonic acid sodium salt；
2) in 60- after sodium peroxydisulfate, neopelex, methyl methacrylate and nano-aluminum hydroxide being mixed
180 DEG C of oil bath reaction 6-12h, then adds ferric trichloride breakdown of emulsion 6-10h, and filtration washing had both obtained modified Nano hydroxide
Aluminium.
A diameter of 60-100nm of the modified aluminum trihydroxide.
The methyl methacrylate, the nano-aluminum hydroxide, the sodium peroxydisulfate, the ferric trichloride and described ten
The mass ratio of dialkyl benzene sulfonic acids sodium is 20-30：40-50：0.2-0.4：1-3：0.1-0.3.
The antiseptic is inorganic silver-series antibacterial agent NOVARON AG300.
The antioxidant is three (2,4- di-t-butyl) phenyl-phosphites, four [β-(3,5- di-tert-butyl-hydroxy phenyls)
Propionic acid] pentaerythritol ester or 1,3,5- trimethyl -2, the one kind or several in 4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyls) benzene
The mixing planted.
The lubricant is one or more in zinc stearate, calcium stearate or potassium stearate.
The preparation method of the scratch-resistant antibacterial high-performance refractory PP composites described in any of the above-described, including following step
Suddenly：
1) weigh 40 parts -60 parts PP, 30 parts of -50 parts of modified aluminum trihydroxides, 8 parts of -12 parts of antiseptics, 0.1 part -
0.5 part of antioxidant, 0.1 part of -0.3 part of mix lubricant simultaneously stir, and obtain compound；
2) by step 1) in the compound extruding pelletization that obtains, that is, obtain PP composites.
Preferably, the step 2) it is specially：By step 1) in the compound that obtains put into the material of double screw extruder
Extruding pelletization in bucket, that is, obtain PP composites, wherein, the double screw extruder includes six humidity provinces sequentially arranged,
One 140～180 DEG C of area's temperature, two 180～200 DEG C of area's temperature, three 180～200 DEG C of area's temperature, four 180～200 DEG C of area's temperature,
Five 180～200 DEG C of area's temperature, six 180～200 DEG C of area's temperature, 180～200 DEG C of head temperature, 200～280r/ of screw speed
min。
The invention has the beneficial effects as follows：
The technical program has been grafted PMMA on nano-aluminum hydroxide, and on nano-aluminum hydroxide surface clad, drop are formed
The surface energy of low nano-aluminum hydroxide particle, is conducive to dispersion of the nano-aluminum hydroxide in PP matrixes, prevents its reunion, carries
The anti-flammability and material physical property of high PP composites.
PMMA engrafted nanometer aluminium hydroxides are conducive to improving the interfacial adhesion of nano-aluminum hydroxide and PP matrixes, and it can be formed
The interface transition layer of modulus gradient, is more beneficial for the transmission of stress, and this is conducive to improving the physical property of material.
The PMMA of the technical program hardness itself is just high, and its presence improves the crocking resistance of PP composites.
The addition of antiseptic NOVARON AG300 improves the anti-microbial property of PP composites.
Specific embodiment
By the following examples describing technical scheme in detail, below example be only it is exemplary, only
Can be used for explaining and illustrating technical scheme, and be not to be construed as the restriction to technical solution of the present invention.
Raw material used is as follows in various embodiments of the present invention：
PP (model Z30S), Daqing Refinery；MMA, Chinese medicines group Solution on Chemical Reagents in Shanghai Co., Ltd；Nano-aluminum hydroxide,
Shandong Zibo Ji headman's trade；Calcium stearate, expects chemical industry in Hubei；Stearic acid sodium, the emerging milky way chemical industry in Hubei；Potassium stearate, Zhengzhou
Nation's promise chemical industry；Antiseptic (model NOVARON AG300), Japanese East Asia Synesis Company；Antioxidant (model Irganox168,
Irganox1010, Irganox1330), Switzerland's Ciba；Neopelex, the triumphant letter chemical industry in Jinan；Sodium peroxydisulfate,
Jinan Feng Le chemical industry；Ferric trichloride, Hubei flourishing age environmental protection science and technology.
Tester used by the present invention is as follows：
ZSK30 type double screw extruders, German W＆P companies；JL-1000 type tensile testing machines, the wide just experiment instrument in Guangzhou
Device company produces；HTL900-T-5B type injection (mo(u)lding) machines, the production of Hai Tai plastics machineries Co., Ltd；XCJ-500 type shock-testings
Machine, the production of Chengde testing machine factory；QT-1196 type tester for elongation, Dongguan City Gao Tai detecting instruments Co., Ltd；QD-GJS-
B12K type homogenizers, Beijing perseverance Order instrument and meter Co., Ltd.
The preparation of modified aluminum trihydroxide first：
Preparation example 1
The preparation method of the modified aluminum trihydroxide, comprises the following steps：
1) weigh a certain amount of methyl methacrylate (MMA), nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride, 12
Sodium alkyl benzene sulfonate；MMA, nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride, the mass ratio of neopelex are 20：
40：0.2：1：0.1.
2) sodium peroxydisulfate, neopelex, MMA, nano-aluminum hydroxide are put into there-necked flask, in 160-
180 DEG C of oil bath reaction 6-12h, then adds ferric trichloride breakdown of emulsion 6-10h, and filtration washing had both obtained modified Nano hydroxide
Aluminium.
Preparation example 2
The preparation method of the modified aluminum trihydroxide, comprises the following steps：
1) weigh a certain amount of methyl methacrylate (MMA), nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride, 12
Sodium alkyl benzene sulfonate；MMA, nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride, the mass ratio of neopelex are 30：
50：0.4：3：0.3.
2) sodium peroxydisulfate, neopelex, MMA, nano-aluminum hydroxide are put into there-necked flask, in 160-
180 DEG C of oil bath reaction 6-12h, then adds ferric trichloride breakdown of emulsion 6-10h, and filtration washing had both obtained modified Nano hydroxide
Aluminium.
Preparation example 3
The preparation method of the modified aluminum trihydroxide, comprises the following steps：
1) weigh a certain amount of methyl methacrylate (MMA), nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride, 12
Sodium alkyl benzene sulfonate；MMA, nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride, the mass ratio of neopelex are 25：
45：0.3：2：0.2.
2) sodium peroxydisulfate, neopelex, MMA, nano-aluminum hydroxide are put into there-necked flask, in 160-
180 DEG C of oil bath reaction 6-12h, then adds ferric trichloride breakdown of emulsion 6-10h, and filtration washing had both obtained modified Nano hydroxide
Aluminium.
Preparation example 4
The preparation method of the modified aluminum trihydroxide, comprises the following steps：
1) weigh a certain amount of methyl methacrylate (MMA), nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride, 12
Sodium alkyl benzene sulfonate；MMA, nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride, the mass ratio of neopelex are 20：
50：0.3：3：0.2.
2) sodium peroxydisulfate, neopelex, MMA, nano-aluminum hydroxide are put into there-necked flask, in 160-
180 DEG C of oil bath reaction 6-12h, then adds ferric trichloride breakdown of emulsion 6-10h, and filtration washing had both obtained modified Nano hydroxide
Aluminium.
Preparation example 5
The preparation method of the modified aluminum trihydroxide, comprises the following steps：
1) weigh a certain amount of methyl methacrylate (MMA), nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride, 12
Sodium alkyl benzene sulfonate；MMA, nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride, the mass ratio of neopelex are 22：
48：0.4：2：0.2.
2) sodium peroxydisulfate, neopelex, MMA, nano-aluminum hydroxide are put into there-necked flask, in 160-
180 DEG C of oil bath reaction 6-12h, then adds ferric trichloride breakdown of emulsion 6-10h, and filtration washing had both obtained modified Nano hydroxide
Aluminium.
Embodiment 1
1) weigh modified aluminum trihydroxide obtained by 40 parts of PP, 30 parts of preparation examples 1,8 parts of NOVARON AG300,0.1
Irganox1330 and 0.4 part of stearic acid sodium of part is mixed and stirred for uniformly, obtaining compound；
2) by step 1) in the compound extruding pelletization that obtains, that is, obtain PP composite P1.
Wherein each area's temperature of double screw extruder and screw speed are respectively：One 140 DEG C of area's temperature, two 180 DEG C of area's temperature,
Three 180 DEG C of area's temperature, four 180 DEG C of area's temperature, five 180 DEG C of area's temperature, six 180 DEG C of area's temperature, 180 DEG C of head temperature, screw rod turns
Fast 200r/min.
Embodiment 2
1) weigh modified aluminum trihydroxide obtained by 60 parts of PP, 50 parts of preparation examples 2,12 parts of NOVARON AG300,
0.2 part of Irganox1330,0.1 part of Irganox1010,0.2 part of Irganox168 and 0.8 part of calcium stearate are mixed and stirred for
It is even, obtain compound；
2) by step 1) in the compound extruding pelletization that obtains, that is, obtain PP composite P2.
Wherein each area's temperature of double screw extruder and screw speed are respectively：One 180 DEG C of area's temperature, two 200 DEG C of area's temperature,
Three 200 DEG C of area's temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 200 DEG C of area's temperature, 200 DEG C of head temperature, screw rod turns
Fast 280r/min.
Embodiment 3
1) weigh modified aluminum trihydroxide obtained by 50 parts of PP, 40 parts of preparation examples 3,10 parts of NOVARON AG300,
0.2 part of Irganox1330,0.1 part of Irganox168,0.3 part of calcium stearate and 0.3 part of stearic acid sodium are mixed and stirred for uniformly,
Obtain compound；
2) by step 1) in the compound extruding pelletization that obtains, that is, obtain PP composite P3.
Wherein each area's temperature of double screw extruder and screw speed are respectively：One 160 DEG C of area's temperature, two 190 DEG C of area's temperature,
Three 190 DEG C of area's temperature, four 190 DEG C of area's temperature, five 190 DEG C of area's temperature, six 190 DEG C of area's temperature, 190 DEG C of head temperature, screw rod turns
Fast 240r/min.
Embodiment 4
1) weigh modified aluminum trihydroxide obtained by 55 parts of PP, 45 parts of preparation examples 4,11 parts of NOVARON AG300,
0.2 part of Irganox1010,0.1 part of Irganox168,0.5 part of stearic acid sodium are mixed and stirred for uniformly, obtaining compound；
2) by step 1) in the compound extruding pelletization that obtains, that is, obtain PP composite P4.
Wherein each area's temperature of double screw extruder and screw speed are respectively：One 175 DEG C of area's temperature, two 200 DEG C of area's temperature,
Three 200 DEG C of area's temperature, four 200 DEG C of area's temperature, five 200 DEG C of area's temperature, six 200 DEG C of area's temperature, 200 DEG C of head temperature, screw rod turns
Fast 230r/min.
Embodiment 5
1) weigh modified aluminum trihydroxide obtained by 45 parts of PP, 40 parts of preparation examples 5,9 parts of NOVARON AG300,0.2
Part Irganox1010,0.1 calcium stearate and 0.5 part of zinc stearate are mixed and stirred for uniformly, obtaining compound；
2) by step 1) in the compound extruding pelletization that obtains, that is, obtain PP composite P5.
Wherein each area's temperature of double screw extruder and screw speed are respectively：One 170 DEG C of area's temperature, two 195 DEG C of area's temperature,
Three 195 DEG C of area's temperature, four 195 DEG C of area's temperature, five 195 DEG C of area's temperature, six 195 DEG C of area's temperature, 195 DEG C of head temperature, screw rod turns
Fast 250r/min.
Comparative example 1
1) weigh 55 parts of PP, 40 parts of nano-aluminum hydroxides, 0.1 part of Irganox1010,0.2 part of Irganox168,0.1 part
Potassium stearate, 0.4 part of zinc stearate are mixed and stirred for uniformly, obtaining compound；
2) by step 1) in the compound extruding pelletization that obtains, that is, obtain PP composite D1.
Wherein each area's temperature of double screw extruder and screw speed are respectively：One 170 DEG C of area's temperature, two 195 DEG C of area's temperature,
Three 195 DEG C of area's temperature, four 195 DEG C of area's temperature, five 195 DEG C of area's temperature, six 195 DEG C of area's temperature, 195 DEG C of head temperature, screw rod turns
Fast 250r/min.
Performance test：
PP composites prepared by above-described embodiment 1-5 and comparative example 1 are made into batten test, test data with injection machine
Such as following table：
The each embodiment of table 1 and comparative example properties of product are tested
As can be seen from the above table, it can also be seen that physical property, crocking resistance, the antibiotic property of embodiment 1-5 from table
Energy, fire resistance are better than comparative example 1.This greatly expands the application of PP composites, has very important significance.
The above is only the description of the preferred embodiment of the present invention, it is noted that due to the finiteness of literal expression, and
Objectively there is unlimited concrete structure, for those skilled in the art, without departing from the principle of the invention
On the premise of, some improvements and modifications can also be made, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of scratch-resistant antibacterial high-performance refractory PP composites, it is characterised in that be made up of the component of following weight portion：
The preparation method of the modified aluminum trihydroxide, comprises the following steps：
1) a certain amount of methyl methacrylate, nano-aluminum hydroxide, sodium peroxydisulfate, ferric trichloride and detergent alkylate sulphur are weighed
Sour sodium；
2) in 60-180 after sodium peroxydisulfate, neopelex, methyl methacrylate and nano-aluminum hydroxide being mixed
DEG C oil bath reaction 6-12h, then add ferric trichloride breakdown of emulsion 6-10h, filtration washing had both obtained modified aluminum trihydroxide.
2. scratch-resistant antibacterial high-performance refractory PP composites according to claim 1, it is characterised in that described modified to receive
A diameter of 60-100nm of rice aluminium hydroxide.
3. scratch-resistant antibacterial high-performance refractory PP composites according to claim 1, it is characterised in that the methyl-prop
The matter of e pioic acid methyl ester, the nano-aluminum hydroxide, the sodium peroxydisulfate, the ferric trichloride and the neopelex
Amount is than being 20-30：40-50：0.2-0.4：1-3：0.1-0.3.
4. scratch-resistant antibacterial high-performance refractory PP composites according to claim 1, it is characterised in that the antiseptic
For inorganic silver-series antibacterial agent NOVARON AG300.
5. scratch-resistant antibacterial high-performance refractory PP composites according to claim 1, it is characterised in that the antioxidant
For three (2,4- di-t-butyl) phenyl-phosphites, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters or
1,3,5- trimethyl -2, the mixing of one or more in 4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyls) benzene.
6. scratch-resistant antibacterial high-performance refractory PP composites according to claim 1, it is characterised in that the lubricant
For one or more in zinc stearate, calcium stearate or potassium stearate.
7. the preparation method of the scratch-resistant antibacterial high-performance refractory PP composites any one of claim 1 to 6, it is special
Levy and be, comprise the following steps：
1) weigh 40 parts -60 parts PP, 30 parts of -50 parts of modified aluminum trihydroxides, 8 parts of -12 parts of antiseptics, 0.1 part -0.5 part
Antioxidant, 0.1 part of -0.3 part of mix lubricant simultaneously stir, and obtain compound；
2) by step 1) in the compound extruding pelletization that obtains, that is, obtain PP composites.
8. the preparation method of scratch-resistant antibacterial high-performance refractory PP composites according to claim 7, it is characterised in that
The step 2) it is specially：By step 1) in the compound that obtains put into extruding pelletization in the hopper of double screw extruder, i.e.,
PP composites are obtained, wherein, the double screw extruder includes six humidity provinces sequentially arranged, area's temperature 140～180
DEG C, two 180～200 DEG C of area's temperature, three 180～200 DEG C of area's temperature, four 180～200 DEG C of area's temperature, five area's temperature 180～200
DEG C, six 180～200 DEG C of area's temperature, 180～200 DEG C of head temperature, 200～280r/min of screw speed.
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Cited By (2)
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|---|---|---|---|---|
| CN107418050A (en) * | 2017-06-21 | 2017-12-01 | 安徽江淮汽车集团股份有限公司 | A kind of high-performance antibiosis PP PA6 composites and preparation method thereof |
| CN112552585A (en) * | 2019-09-26 | 2021-03-26 | 合肥杰事杰新材料股份有限公司 | Modified polypropylene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107418050A (en) * | 2017-06-21 | 2017-12-01 | 安徽江淮汽车集团股份有限公司 | A kind of high-performance antibiosis PP PA6 composites and preparation method thereof |
| CN112552585A (en) * | 2019-09-26 | 2021-03-26 | 合肥杰事杰新材料股份有限公司 | Modified polypropylene and preparation method thereof |
| CN112552585B (en) * | 2019-09-26 | 2022-12-06 | 滁州杰事杰新材料有限公司 | Modified polypropylene and preparation method thereof |
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