CN104845410A - Preparation and application of plastic modifier - Google Patents
Preparation and application of plastic modifier Download PDFInfo
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- CN104845410A CN104845410A CN201510154125.4A CN201510154125A CN104845410A CN 104845410 A CN104845410 A CN 104845410A CN 201510154125 A CN201510154125 A CN 201510154125A CN 104845410 A CN104845410 A CN 104845410A
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- bucket
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- plastic modifier
- inorganic powders
- plastic
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- 229920003023 plastic Polymers 0.000 title claims abstract description 41
- 239000004033 plastic Substances 0.000 title claims abstract description 41
- 239000003607 modifier Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 4
- -1 titanate ester Chemical class 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 238000011081 inoculation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000012760 heat stabilizer Substances 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000012785 packaging film Substances 0.000 description 4
- 229920006280 packaging film Polymers 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 229920006262 high density polyethylene film Polymers 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention discloses a method for preparing a plastic modifier with desirable dispersibility, characterized by comprising the following steps of: S1, measuring the particle size and the moisture content of inorganic powders; S2, selecting inorganic powders that are 200nm-300nm in average particle size and lower than 0.25% in moisture content from the inorganic powders in S1; S3, adding the inorganic powders in S2 into a high speed stirring barrel, and heating the system temperature to 100-105 DEG C to stir the inorganic powders for 7 minutes; S4, spraying active components to the inorganic powders in S3 during stirring, wherein the mass ratio of the active components to the inorganic powders is 0.7:100, and the spraying time is 10-15 minutes; S5, performing cooling to reach the room temperature, and discharging the material. With the plastic modifier being the main material, carrier resin, a dispersant, a coupling agent, a heat stabilizer and an antioxidant are added, and after stirring and reaction, the system is added into granulating equipment for a high-temperature extruding process, so that the master batch is obtained. The plastic modifier disclosed by the present invention has desirable dispersibility. The master batch prepared by using the plastic modifier disclosed by the present invention as the main material is applied to plastic products, thereby achieving the effects of high strength and high transparency.
Description
Technical field
The present invention relates to a kind of preparations and applicatio of plastic modifier, particularly relate to preparation and the application thereof of a kind of polyethylene or polypropylene-base plastic modifier.
Background technology
Plastics refer to resin (or using monomer direct polymerization in the course of processing) for main component, with additives such as softening agent, weighting agent, lubricant, tinting materials for ancillary component, through the plastic material of machine-shaping, or the rigid material that curing cross-linked is formed.Plastics are the products in 20th century, and since being developed, the purposes of each side is increasingly extensive.
Polyethylene and polypropylene-base plastics belong to the category of general-purpose plastics, and output is large, and purposes is wide, and its topmost purposes is on packaging film.Since " limit is purchased and is made ", client to the transparency of packaging film and requirement of strength more and more higher.In this context, the use of traditional market calcium carbonate, talcpowder filled masterbatches cannot meet the demand of client.In addition, common plastic film packaging market price competition is very fierce, and develop a kind of raw material production cost that can reduce product, the type material can enhanced product performance again just seems particularly important.
Summary of the invention
In order to solve the problems of the prior art, the object of this invention is to provide a kind of preparation method and application thereof of plastic modifier, the increase product strength, the master batch of reduction goods cost and the preparation method of master batch that obtain for main body with this plastic modifier are provided simultaneously.
To achieve these goals, the technical solution used in the present invention:
A preparation method for plastic modifier, is characterized in that, comprises the steps:
S1, the particle diameter measuring inorganic powder and water ratio;
S2, select median size in S1 to be 200nm-300nm, water ratio lower than 0.25% inorganic powder;
S3, join in high-speed stirring bucket by the inorganic powder in S2, heating systems temperature to 100 DEG C-105 DEG C, stirs 7 minutes;
S4, in S3, spray activeconstituents while stirring, the mass ratio of activeconstituents and inorganic powder is 0.7:100, and spray time is 10-15 minute;
S5, be cooled to room temperature, discharge material.
Wherein, described inorganic powder is nano barium sulfate or nano-calcium carbonate.
Wherein, described activeconstituents is stearates tensio-active agent or titanate ester tensio-active agent.
Wherein, described sprinkling equipment is high speed mixing smelting machine.
The plastic modifier powder application obtained by preceding method is in the master batch preparing the gaining in strength of transparent packaging film, biological degradation shopping bag, shopping bag for supermarket, bag on roll, quiet tubing, crystalline p p sheet and polypropylene board material products, glossiness, transparency.
The master batch that the plastic modifier powder obtained with preceding method obtains for main body, it is characterized in that, comprise: the plastic modifier powder of 75%-80%, the vector resin of 12%-18%, the dispersion agent of 3%-4%, coupling agent 0.5%-3%, thermo-stabilizer 0.1%-1%, oxidation inhibitor 0.05%-2%.
Wherein, described vector resin is one or more in linear polyethylene, metallocene PE, polyethylene elastomer; Described dispersion agent be polyethylene wax, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate multipolymer one or more; Described coupling agent is titanate coupling agent or silane coupling agent; Described thermo-stabilizer is stearate, preferably calcium stearate or Zinic stearas; Described oxidation inhibitor is 1010 or 168.
Prepare the method for aforementioned master batch, it is characterized in that, comprise the steps:
A1, take each material according to aforesaid mass percent;
A2, be placed in A bucket by plastic modifier powder, vector resin is placed in B bucket, and dispersion agent, coupling agent, thermo-stabilizer and oxidation inhibitor are placed in C bucket;
A3, open flowrate control valve, by A bucket, the material in B bucket and C bucket joins high-speed stirring bucket simultaneously, and the flow being 520-560kg/h, B bucket by the flow of conputer controlled A bucket is the flow of 130-160kg/h, C bucket is 70-80kg/h, stirring reaction;
A4, the mixture in A3 is added in granulating equipment, extrude at 110 DEG C-160 DEG C, obtain master batch finished product.
Wherein, the temperature of reaction in described steps A 3 is 80-120 DEG C, and the reaction times is 0.5-1h.
Wherein, described granulating equipment is that metering twin screw Dual inoculation vowed by computer.
The plastic modifier good dispersity that the present invention obtains, adds in plastics the brilliant point that significantly can reduce plastics to; With plastic modifier of the present invention for main body prepares master batch, be applied in the goods such as transparent packaging film, biological degradation shopping bag, shopping bag for supermarket, the quiet tubing of bag on roll, crystalline p p sheet and polypropylene board, goods realize the effect of high strength and high-clarity, plastic modifier price of the present invention is low simultaneously, reduces the production cost of plastics; The master batch that the present invention obtains is applied to plastics, can realize the recycling of goods, meets the demand of society low-carbon environment-friendly.
Embodiment
One. the preparation of plastic modifier
First, joined by inorganic powder in high-speed stirring bucket, heating systems temperature to 100 DEG C-105 DEG C, stirs 7 minutes; Then in high-speed stirring bucket, spray activeconstituents while stirring, spray time is 10-15 minute; Be cooled to room temperature, discharge material.Described inorganic powder is commercially available prod, and median size is 200nm-300nm, and water ratio is lower than 0.25%; Described inorganic powder is nano barium sulfate or nano-calcium carbonate; Described activeconstituents is stearic acid or titanate ester tensio-active agent.
Table 1:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Activeconstituents | Stearic acid tensio-active agent | Titanate ester tensio-active agent | Stearic acid tensio-active agent | Titanate ester tensio-active agent |
| Spray time/minute | 10 | 12 | 15 | 15 |
| Inorganic powder composition | Nano barium sulfate | Nano-calcium carbonate | Nano-calcium carbonate | Nano barium sulfate |
| Inorganic powder median size/nm | 200 | 267 | 250 | 300 |
| Inorganic powder water ratio | 0.2% | 0.25% | 0.2% | 0.23% |
The plastic modifier prepared by embodiment 1-4 adds in plastic carrier, makes lamellar body, finds lamellar body all exists without brilliant point, and obtained plastic modifier good dispersity is described.
Two. be that main body prepares master batch with plastic modifier
Each material is taken according to the mass percent of embodiment 5-8; Then be placed in A bucket by the plastic modifier powder prepared in embodiment 1-4, vector resin is placed in B bucket, and dispersion agent, coupling agent, thermo-stabilizer and oxidation inhibitor are placed in C bucket; Open flowrate control valve, by A bucket, the material in B bucket and C bucket joins high-speed stirring bucket simultaneously, and the flow being 520-560kg/h, B bucket by the flow of conputer controlled A bucket is the flow of 130-160kg/h, C bucket is 70-80kg/h, stirring reaction; Reacted mixture is added in granulating equipment, extrudes at 110 DEG C-160 DEG C, obtain master batch finished product.Described vector resin is one or more in linear polyethylene, metallocene PE, polyethylene elastomer; Described dispersion agent be polyethylene wax, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate multipolymer one or more; Described coupling agent is titanate coupling agent or silane coupling agent; Described thermo-stabilizer is stearate, preferably calcium stearate or Zinic stearas; Described oxidation inhibitor is 1010 or 168.
Table 2:
In order to illustrate that the master batch prepared in embodiment 5-8 is applied in goods better, realize the effect of goods high strength and high-clarity, for embodiment 5, the HDPE film under the different master batch addition of DCO, ldpe film, the performance index of PP sheet material.
Table 3: under different master batch addition, the performance parameter variations of HDPE film
| Master batch addition | Tensile strength/Mpa | Transmittance |
| 0 | 24.6 | 94% |
| 3% | 25.2 | 94% |
| 6% | 26.0 | 94% |
| 9% | 26.5 | 94% |
| 12% | 27.3 | 90% |
Table 4: under different master batch addition, the performance parameter variations of ldpe film
| Master batch addition | Tensile strength/Mpa | Transmittance |
| 0 | 20.8 | 96% |
| 3% | 22.1 | 96% |
| 6% | 23.5 | 96% |
| 9% | 24.9 | 96% |
| 12% | 24.1 | 92% |
Table 5: under different master batch addition, the performance parameter variations of PP sheet material
| Master batch addition | Tensile strength/Mpa | Transmittance |
| 0 | 30.2 | 90% |
| 3% | 32.1 | 90% |
| 6% | 33.5 | 90% |
| 9% | 34.6 | 90% |
| 12% | 36.0 | 86% |
Table 6: under different master batch addition, HDPE film, ldpe film, the Cost comparisons of PP sheet material
| Master batch addition | HDPE | LDPE | PP sheet material | Total cost yuan/ton |
| 0% | 100% | 12000 | ||
| 3% | 97% | 11563 | ||
| 6% | 94% | 10950 | ||
| 9% | 91% | 10358 | ||
| 12% | 88% | 9873 | ||
| 0% | 100% | 12800 | ||
| 3% | 97% | 12085 | ||
| 6% | 94% | 11587 | ||
| 9% | 91% | 10983 | ||
| 12% | 88% | 9984 | ||
| 0% | 100% | 10800 | ||
| 3% | 97% | 10248 | ||
| 6% | 94% | 9843 | ||
| 9% | 91% | 9504 | ||
| 12% | 88% | 9258 |
Above-mentioned embodiment is exemplary, is to enable those skilled in the art understand this patent better, can not be interpreted as it is restriction this patent being comprised to scope; As long as according to this patent disclose any equivalent change done or the modification of spirit, all fall into the scope that this patent comprises.
Claims (9)
1. a preparation method for plastic modifier, is characterized in that, comprises the steps:
S1, the particle diameter measuring inorganic powder and water ratio;
S2, select median size in S1 to be 200nm-300nm, water ratio lower than 0.25% inorganic powder;
S3, join in high-speed stirring bucket by the inorganic powder in S2, heating systems temperature to 100 DEG C-105 DEG C, stirs 7 minutes;
S4, in S3, spray activeconstituents while stirring, the mass ratio of activeconstituents and inorganic powder is 0.7:100, and spray time is 10-15 minute;
S5, be cooled to room temperature, discharge material.
2. the preparation method of plastic modifier as claimed in claim 1, it is characterized in that, described inorganic powder is nano barium sulfate or nano-calcium carbonate.
3. the preparation method of plastic modifier as claimed in claim 1, it is characterized in that, described activeconstituents is stearates tensio-active agent or titanate ester tensio-active agent.
4. the preparation method of plastic modifier as claimed in claim 1, it is characterized in that, described sprinkling equipment is high speed mixing smelting machine.
5. the master batch that the plastic modifier powder obtained with the method for claim 1 obtains for main body, it is characterized in that, comprise: the plastic modifier powder of 75%-80%, the vector resin of 12%-18%, the dispersion agent of 3%-4%, coupling agent 0.5%-3%, thermo-stabilizer 0.1%-1%, oxidation inhibitor 0.05%-2%.
6. master batch as claimed in claim 5, it is characterized in that, described vector resin is one or more in linear polyethylene, metallocene PE, polyethylene elastomer; Described dispersion agent be polyethylene wax, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate multipolymer one or more; Described coupling agent is titanate coupling agent or silane coupling agent; Described thermo-stabilizer is stearate, preferably calcium stearate or Zinic stearas; Described oxidation inhibitor is 1010 or 168.
7. prepare the method for master batch according to claim 5, it is characterized in that, comprise the steps:
A1, mass percent according to claim 5 take each material;
A2, be placed in A bucket by plastic modifier powder, vector resin is placed in B bucket, and dispersion agent, coupling agent, thermo-stabilizer and oxidation inhibitor are placed in C bucket;
A3, open flowrate control valve, by A bucket, the material in B bucket and C bucket joins high-speed stirring bucket simultaneously, and the flow being 520-560kg/h, B bucket by the flow of conputer controlled A bucket is the flow of 130-160kg/h, C bucket is 70-80kg/h, stirring reaction;
A4, the mixture in A3 is added in granulating equipment, extrude at 110 DEG C-160 DEG C, obtain master batch finished product.
8. prepare the method for master batch as claimed in claim 7, it is characterized in that, the temperature of reaction in described steps A 3 is 80-120 DEG C, and the reaction times is 0.5-1h.
9. prepare the method for master batch as claimed in claim 7, it is characterized in that, described granulating equipment is that metering twin screw Dual inoculation vowed by computer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510154125.4A CN104845410B (en) | 2015-04-02 | 2015-04-02 | A kind of preparation and its application of plastic modifier |
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| CN201510154125.4A CN104845410B (en) | 2015-04-02 | 2015-04-02 | A kind of preparation and its application of plastic modifier |
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| CN104845410A true CN104845410A (en) | 2015-08-19 |
| CN104845410B CN104845410B (en) | 2018-10-26 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543558A (en) * | 2016-10-17 | 2017-03-29 | 江西广源新材料有限公司 | A kind of polypropylene filler parent granule and preparation method thereof |
| CN106752103A (en) * | 2016-12-14 | 2017-05-31 | 广东圆融新材料有限公司 | A kind of preprocess method of blanc fixe |
| CN108892846A (en) * | 2018-06-28 | 2018-11-27 | 庆云诺鑫塑胶新材料有限公司 | Degradable masterbatch of nano biological and preparation method thereof |
| CN109021354A (en) * | 2018-06-28 | 2018-12-18 | 庆云诺鑫塑胶新材料有限公司 | Blown film degradable masterbatch and preparation method thereof |
| CN109161150A (en) * | 2018-08-22 | 2019-01-08 | 扬州朗劲塑胶实业有限公司 | A kind of foaming master batch and preparation method thereof |
| CN110484022A (en) * | 2019-09-09 | 2019-11-22 | 青州宇信钙业股份有限公司 | A kind of production technology of the nanometer calcium carbonate of transparent membrane |
| CN111574853A (en) * | 2020-06-09 | 2020-08-25 | 江苏群鑫粉体科技股份有限公司 | Modified barium sulfate for heavy-duty anticorrosive paint |
| CN112980216A (en) * | 2021-03-09 | 2021-06-18 | 浙江达尔美塑胶有限公司 | Modified titanium dioxide and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543558A (en) * | 2016-10-17 | 2017-03-29 | 江西广源新材料有限公司 | A kind of polypropylene filler parent granule and preparation method thereof |
| CN106752103A (en) * | 2016-12-14 | 2017-05-31 | 广东圆融新材料有限公司 | A kind of preprocess method of blanc fixe |
| CN108892846A (en) * | 2018-06-28 | 2018-11-27 | 庆云诺鑫塑胶新材料有限公司 | Degradable masterbatch of nano biological and preparation method thereof |
| CN109021354A (en) * | 2018-06-28 | 2018-12-18 | 庆云诺鑫塑胶新材料有限公司 | Blown film degradable masterbatch and preparation method thereof |
| CN109161150A (en) * | 2018-08-22 | 2019-01-08 | 扬州朗劲塑胶实业有限公司 | A kind of foaming master batch and preparation method thereof |
| CN110484022A (en) * | 2019-09-09 | 2019-11-22 | 青州宇信钙业股份有限公司 | A kind of production technology of the nanometer calcium carbonate of transparent membrane |
| CN111574853A (en) * | 2020-06-09 | 2020-08-25 | 江苏群鑫粉体科技股份有限公司 | Modified barium sulfate for heavy-duty anticorrosive paint |
| CN112980216A (en) * | 2021-03-09 | 2021-06-18 | 浙江达尔美塑胶有限公司 | Modified titanium dioxide and preparation method and application thereof |
| CN112980216B (en) * | 2021-03-09 | 2022-04-26 | 浙江达尔美塑胶有限公司 | Modified titanium dioxide and preparation method and application thereof |
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| CN104845410B (en) | 2018-10-26 |
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