CN1039221C - Granular high-active zinc oxide - Google Patents
Granular high-active zinc oxide Download PDFInfo
- Publication number
- CN1039221C CN1039221C CN95117887A CN95117887A CN1039221C CN 1039221 C CN1039221 C CN 1039221C CN 95117887 A CN95117887 A CN 95117887A CN 95117887 A CN95117887 A CN 95117887A CN 1039221 C CN1039221 C CN 1039221C
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- CN
- China
- Prior art keywords
- active
- active zinc
- manufacture method
- zinc oxide
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims description 27
- 229910052725 zinc Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000013543 active substance Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 125000005908 glyceryl ester group Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- -1 comprise-OH Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 238000005469 granulation Methods 0.000 abstract description 13
- 230000003179 granulation Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003292 glue Substances 0.000 abstract description 7
- 239000000428 dust Substances 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 3
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010074 rubber mixing Methods 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 2
- 229920001971 elastomer Polymers 0.000 description 7
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 229940024464 emollients and protectives zinc product Drugs 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention provides granular zinc oxide with high activity, which is manufactured by adding an adhesion dispersing agent or a surface modifying agent by a screw extruder. Because the adhesion dispersing agent is added in the granulation course, the problems that the zinc oxide with high activity, which is not granulated, generates flying dust, sticks on a roller and does not uniformly dispersed during rubber mixing are solved; when the surface modifying agent is added for granulation, the activation of the activated zinc oxide in glue is improved, which has important functions for the popularization and the application of the zinc oxide with high activity.
Description
The present invention relates to high-active zinc oxide, specifically, relate to manufacture method of a kind of granular high-active zinc oxide and products thereof.
Usually often use the powdered active zinc flower in the rubber industry, because particle diameter carefully has very big specific surface area, its specific surface area is bigger about 20 times than common zinc oxide approximately, thereby can give full play to its active function in rubber, the purpose that reach decrement, improves performance, reduces cost.But because powdered active zinc flower particle diameter is thin, incident is its calendering process poor-performing in rubber, and relatively distinct issues are: dust from flying when mixing, roll banding and the unequal shortcoming of dispersion are restricted the effect of active zinc flower.
The object of the present invention is to provide manufacture method of a kind of granular high-active zinc oxide and products thereof, this granular high-active zinc oxide of producing through adding bonding dispersion agent and tensio-active agent, it is constant not only to have kept original activity, and because the effect of dispersion agent and promoting agent, eliminated its dust from flying and roll banding phenomenon in rubber mixing process, improved the labor condition of compounding rubber, and the dissemination in glue is significantly improved.
The manufacture method of granular high-active zinc oxide provided by the present invention, be on the basis that original high-active zinc oxide is produced, improve a kind of novel granulation product of invention, promptly be by with powdered activated zinc oxide further in accordance with regulations prescription add the bonding dispersion agent, stirring is obtained by the screw extrusion press manufacturing, and its technological process comprises mixing, screw rod extruding pelletization, drying and other steps.
Granular high-active zinc oxide provided by the present invention, be in powdered activated zinc oxide further in accordance with regulations prescription add the bonding dispersion agent, can also add tensio-active agent again, obtain active higher granular high-active zinc oxide.
In granular high-active zinc oxide provided by the present invention, wherein said bonding dispersion agent is the oligopolymer that has or do not have specific functional groups, functional group can be carboxyl or hydroxyl, the molecular weight of oligopolymer is 1000-10000, be preferably 3000-5000: the amount of the dispersion agent that bonds in addition (weight percent) is about the 10%-50% of high-active zinc oxide amount, preferably 15%-30%.
In granular high-active zinc oxide provided by the present invention, wherein said oligopolymer comprises polyhutadiene, polyisobutene or carboxy terminatedpolybutadiene, hydroxyl polyhutadiene.
In granular high-active zinc oxide provided by the present invention, wherein said tensio-active agent, one end is hydrophilic polar functional group, as-OH ,-COOH ,-COOR, the other end is hydrophobic paraffinic hydrocarbons, carbon number≤18, preferably carbon number is 3-8: the amount of surface-modifying agent (weight percent) is about the 2%-10% of high-active zinc oxide amount in addition, is preferably 3%-5%.
In granular high-active zinc oxide provided by the present invention, wherein said tensio-active agent can be that carbon number is the carboxylic acid of 3-8 and in the corresponding glyceryl ester one or more thereof, as in propionic acid, butyric acid, caproic acid and the sad and corresponding glyceryl ester one or more.
The technology of granulation involved in the present invention or modification granulation is:
Active zinc flower with specified amount drops into mixing tank earlier; constantly under the agitation condition required bonding dispersion agent and tensio-active agent are being joined in the zinc oxide; add an amount of polyhydric treating compound of being with again; after stirring; discharge enters the tablets press hopper, by screw extrusion press the zinc oxide material that mixes is extruded with the grain column subsequently.Vulcanize the drying bed drying and granulating column pellet through vibration, directly packing forms (interior is that plastics bag, outer packaging are the garden cardboard cylinder).
Further specify below in conjunction with preferred embodiment.
Embodiment 1:
With 100kg specific surface area 〉=45m
2The active zinc flower of/g adds in the taper mixing tank; under continuous agitation condition; with the 20kg molecular weight is that the oligopolymer of 3000-5000 such as the polyhutadiene of polyhutadiene, polyisobutene or hydroxyl or carboxyl spray into vaporific after suitably heating; after stirring under 80-120 ℃; add and be with polyhydric treating compound in right amount; to impel oligopolymer further to be uniformly dispersed; scattered material directly enters the tablets press hopper; by screw extrusion press it is extruded with the garden column, enter vibration sulfuration drying bed.Under vibration and hot blast drive, the gradually grow up columnar-shaped particle of about 2-4mm of garden column active zinc flower, moisture≤1%.Vulcanize the other end collecting packing of drying bed at last in vibration.
Embodiment 2:
With 100kg specific surface area 〉=45m
2The active zinc flower of/g adds in the taper mixing tank, under constantly stirring with the 3kg tensio-active agent, for example the carboxylic acid of carbon number≤18 or caproic acid are sprayed into vaporific through suitably heating the back by hopper, allow material continue down to stir 30 minutes at 80-120 ℃, make the active oxidation zinc surface play abundant modification, be oligopolymer such as the polyhutadiene of 3000-5000 again with the 20kg molecular weight, the polyhutadiene of polyisobutene or hydroxyl or carboxyl is through suitably spraying into vaporific after the heating, below press the same operation steps of embodiment 1, with above-mentioned material corning columnar-shaped particle, water content≤1%.
Embodiment 3
The effect simultaneous test.
Active zinc flower after embodiment 1 and 2 granulations of embodiment and the active zinc flower before the granulation are added respectively in the following rubber equally, compare every rerum natura of its sizing material again.The cooperation of sizing material is (weight): natural rubber 100; Stearic acid 3.0; Promotor 0.6; Sulphur 2.5; N330 carbon black 50.0; Zinc oxide 20; Granular zinc oxide contrast experiment with pulverous active zinc flower commonly used and the invention process 1 and 2 records sizing material physicals such as following table:
| Zinc oxide kind project | Powdered active zinc flower | The ordinary granular active zinc flower | The granular active zinc flower of modification |
| 151 ℃ of X of cure conditions | 20’ 60’ | 20’ 60’ | 20’ 60’ |
| Hardness (Shao A) | 66 66 | 66 65 | 66 65 |
| Breaking tenacity (Mpa) | 25.7 19.4 | 25.8 19.0 | 25.6 21.0 |
| Tensile yield % | 472 402 | 460 418 | 462 402 |
| 300% tensile modulus (Mpa) | 15.5 12.5 | 15.9 12.7 | 15.6 13.8 |
| Tension set % | 30 15 | 28 15 | 26 15 |
Annotate: cure conditions is 151 ℃, 20 ' and 60 ' contrast
Comparing result shows: through common granulation the active function of active zinc flower in glue do not influenced, and the active function of the high-active zinc oxide after the surface modification granulation in glue strengthens to some extent.The mechanical properties of rubber compound that is reflected in over cure point increases (60 ').Experimental results show that: no matter be the common granulation active zinc flower that embodiment 1 makes, still granular active zinc flower more is good at being dispersed in the glue than prilling powder shape active zinc flower not in mixing process behind the activation modification made of embodiment 2, shortened the dispersion required time: also eliminate dust from flying and roll banding phenomenon in mixing, improved the sanitary condition of mixing environment; Further stablized the decrement effect of active zinc flower in glue, good social benefit and economic benefit have been arranged.
The present invention is by adding bonding dispersion agent or tensio-active agent, make by screw extrusion press in the method for particulate state high-active zinc oxide, owing to add the bonding dispersion agent in the granulation, granulation high-active zinc oxide dust from flying, roll banding and inhomogeneous dispersive problem when mixing in rubber have been improved not; When the interpolation tensio-active agent carries out granulation, also improved the activation of active zinc flower in glue simultaneously, applying of high-active zinc oxide had very vital role.
Claims (10)
1, a kind of manufacture method of granular high-active zinc oxide, it is characterized in that this manufacture method comprises that the active zinc flower with certainweight drops in the mixing tank, adding vaporific bonding dispersion agent that sprays into after heating is the 10-50 (% weight) and the tensio-active agent 2-10 (% weight) of this active zinc flower under agitation condition
Add again and be with polyhydric treating compound in right amount, under 80-120 ℃ of condition, after stirring, send into the tablets press hopper; By screw extrusion press the active zinc flower material that mixes is extruded with the grain column subsequently; Through vibration sulfuration drying bed drying, make moisture≤1% again, make granular high-active zinc oxide.
2, manufacture method according to claim 1, it is characterized in that this bonding dispersion agent comprises the oligopolymer that has or do not have functional group, this functional group comprises polyhutadiene, polyisobutene or carboxy terminatedpolybutadiene, hydroxyl polyhutadiene, and molecular weight is 1000-10000.
3, manufacture method according to claim 1 is characterized in that an end of this tensio-active agent is hydrophilic polar functional group, comprise-OH ,-COOH ,-COOR, the other end is hydrophobic paraffinic hydrocarbons, comprises the saturated chain alkyl of carbon number≤18.
4, manufacture method according to claim 1 is characterized in that this tensio-active agent is that carbon number is the carboxylic acid of 3-8 and in the corresponding glyceryl ester one or more thereof, comprises in propionic acid, butyric acid, caproic acid and the sad and corresponding glyceryl ester one or more.
5, manufacture method according to claim 1, the length that it is characterized in that this column is 2-4mm.
6, manufacture method according to claim 1, the molecular weight that it is characterized in that this oligopolymer is 3000-5000.
7, manufacture method according to claim 1 is characterized in that the 15-30 (% weight) of this bonding dispersion agent for this active zinc flower.
8, manufacture method according to claim 1 is characterized in that the 3-5 (% weight) of this tensio-active agent for this active zinc flower.
9, manufacture method according to claim 1 is characterized in that this tensio-active agent can not add.
10, a kind of granular high-active zinc oxide product, it is characterized in that this product makes with the described method of claim 1, be included in and add 10-50 (% weight) and the tensio-active agent 2-10 (% weight) of bonding dispersion agent in (weight) active zinc flower of certainweight for this active zinc flower, the length of making is 2-4mm grain column, its moisture≤1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117887A CN1039221C (en) | 1995-12-11 | 1995-12-11 | Granular high-active zinc oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117887A CN1039221C (en) | 1995-12-11 | 1995-12-11 | Granular high-active zinc oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1130154A CN1130154A (en) | 1996-09-04 |
| CN1039221C true CN1039221C (en) | 1998-07-22 |
Family
ID=5081424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95117887A Expired - Fee Related CN1039221C (en) | 1995-12-11 | 1995-12-11 | Granular high-active zinc oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1039221C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235222B (en) * | 2007-12-28 | 2010-12-01 | 太仓诚信化工有限公司 | Preparation method of zinc oxide for rubber |
| CN101353448B (en) * | 2008-09-13 | 2010-09-29 | 山东东高纳米科技有限公司 | Dustfree demolding agent for high polymer elastic particle |
| CN105367924B (en) * | 2015-12-07 | 2018-08-10 | 中国石油天然气股份有限公司 | Granulated plastic additive and preparation method and application thereof |
| CN110317382B (en) * | 2019-06-14 | 2021-05-14 | 华南理工大学 | Environment-friendly rubber vulcanization activator and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106030A (en) * | 1993-10-20 | 1995-08-02 | 埃勒夫阿托化学有限公司 | Unorganic particles coated with elastic material |
-
1995
- 1995-12-11 CN CN95117887A patent/CN1039221C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106030A (en) * | 1993-10-20 | 1995-08-02 | 埃勒夫阿托化学有限公司 | Unorganic particles coated with elastic material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1130154A (en) | 1996-09-04 |
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