CN105819678A - Modified high-length/diameter ratio wollastonite fiber and preparation method thereof - Google Patents
Modified high-length/diameter ratio wollastonite fiber and preparation method thereof Download PDFInfo
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- CN105819678A CN105819678A CN201610123313.5A CN201610123313A CN105819678A CN 105819678 A CN105819678 A CN 105819678A CN 201610123313 A CN201610123313 A CN 201610123313A CN 105819678 A CN105819678 A CN 105819678A
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- wollastonite
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
Abstract
The invention relates to a modified high-length/diameter ratio wollastonite fiber and a preparation method thereof. The method comprises a high-length/diameter ratio wollastonite preparation process A, a high-length/diameter ratio wollastonite pretreatment process B and a high-length/diameter ratio wollastonite modifying process C; and the high-length/diameter ratio wollastonite preparation process A comprises the following steps: 1, crushing an ore sample to obtain a primary product; and 2, screening the primary product to obtain a wollastonite sub-quality product with the particle size of 15-50 meshes. Compared with the prior art, the preparation method has the following advantages: a hydroxy active group on the surface of wollastonite reacts with the functional group of an added modifier to form a stable reaction group, so stable modification of the high-length/diameter ratio wollastonite fiber is realized, the compatibility between the high-length/diameter ratio wollastonite and a polymer material is improved, and the mechanical performances of the wollastonite fiber are improved; and the preparation method also has the advantages of simple production technology, stable product quality and low production cost.
Description
Technical field
The present invention relates to inorganic material-modified field, specifically, relate to a kind of modified wollastonite with high length-diameter ratio fiber and preparation method thereof.
Background technology
The superfine product that current nonmetal wollastonite is machined, modification technology produces, is widely used as filler or the coating of the high-grade product such as papermaking, rubber, plastics, pottery, paint, cosmetics and aerospace industry.
Chinese patent 201010109571.0 discloses a kind of employing calcium hydroxide and sodium silicate solution synthetic silicic acid hydrate of calcium under weak basic condition, it is dried through washing again, calcination processing under an inert atmosphere, then use coupling agent that powder body is carried out surface modification treatment, finally carry out polish and obtain wollastonite powder body, use the method productive manpower synthesis modification wollastonite fibre cost high, more natural wollastonite processing cost is up to 10 20 times, product is mainly used in the higher-end businesses such as electronics, and the application of its popularity is poor.
Chinese patent 200910042410.1 discloses a kind of employing coveredwith nanometer calcium carbonate, apply the Technology of coupling agent modified wollastonite fibre, wollastonite fibre cost more natural wollastonite processing cost height 3-10 times that this technology is produced, product processes is complicated, operation easier is bigger, the more difficult control of quality stability, has not yet to see it and promotes.
Chinese patent 201110101416.9 discloses the preparation technology of a kind of cationic wollastonite with high length-diameter ratio fiber using amidic-salt modification, the wollastonite fibre that this technology is produced is relatively costly, and react in solid system, effective, uniformly modification to wollastonite with high length-diameter ratio fiber can not be realized, and operation easier is relatively big, has not yet to see it and be widely popularized.
Summary of the invention
It is an object of the invention to the deficiency overcoming existing production technology to exist, the modified silicon ash mineral wool of a kind of high length-diameter ratio, low cost is provided, to adapt to the application demand in the fields such as macromolecular material, rubber, asbestos, paint, improve the hardness of goods, bending strength, impact strength, the heat stability of raising material and dimensional stability, have a wide range of applications field and application prospect.
It is a further object to provide the preparation method of above-mentioned modified wollastonite with high length-diameter ratio fiber.
Concrete technical solution is as follows:
A kind of modified wollastonite with high length-diameter ratio fiber and preparation method thereof: include wollastonite with high length-diameter ratio preparation section A, wollastonite with high length-diameter ratio pretreatment process B, wollastonite with high length-diameter ratio modified process C;
Wollastonite with high length-diameter ratio preparation section A comprises the following steps:
Sample ore is pulverized by step (1), obtains primary product；
Primary product is sieved by step (2), has obtained the wollastonite sub-quality products that particle diameter is 15--50 mesh；
Wollastonite with high length-diameter ratio pretreatment process B comprises the following steps:
The particle diameter that wollastonite with high length-diameter ratio preparation section A described in wollastonite with high length-diameter ratio preparation section A obtains is that 15 50 mesh sub-quality products stir 3 40 hours in 35 90 DEG C for 1:3 1:20 in mass ratio with pretreating agent by step (1), obtains suspension；
The suspension that step (1) described in wollastonite with high length-diameter ratio preparation section B obtains is filtered and reclaims pretreating agent and obtains masterbatch by step (2)；
Masterbatch after step (2) filtration described in wollastonite with high length-diameter ratio preparation section B is put in vacuum drying oven and is dried 2 45 hours in 40 80 DEG C by step (3), obtains pretreated wollastonite with high length-diameter ratio after crushing, sieving；
Wollastonite with high length-diameter ratio modified process C comprises the following steps:
The pretreated wollastonite with high length-diameter ratio that step (3) described in wollastonite with high length-diameter ratio preparation section B obtains is mixed in the solvent of 100 weight portions, stirs for 100:1 100:1.5 with modifying agent by step (1) in mass ratio, it is warming up to 35 60 DEG C after adding catalyst stir 15 hours, completes the modification of wollastonite with high length-diameter ratio；
The modified wollastonite with high length-diameter ratio that step (1) described in wollastonite with high length-diameter ratio preparation section C is obtained by step (2) through desolventizing, dry, crush, sieve after, be 120-600 mesh by particle diameter, carry out classification according to GB/T 1345-2005 standard；
Step (3) the modified wollastonite with high length-diameter ratio that step (2) described in wollastonite with high length-diameter ratio preparation section C obtains is analyzed inspection, qualified after pack warehouse-in, obtained finished product.
Described pretreating agent is the mixture of one or more in dimethyl sulfoxide, hydrazine, potassium acetate, sodium acetate, ammonium acetate, ammonium chloride；
Described modifying agent is the mixture of one or more in silane coupler, titanate coupling agent, amidic-salt, isocyanates, tripolycyanamide cyanate；
Described catalyst is the mixture of one or more in triethylene diamine, diethylamine, stannous octoate, dibutyl tin laurate.
The present invention is compared with prior art, after preprocessed dose of wollastonite surface processes, the functional group enabling to the hydroxyl reactive group on wollastonite surface and the modifying agent of addition reacts, form stable reactive group, achieve the stable modification of wollastonite with high length-diameter ratio fiber, drastically increase the compatibility of wollastonite with high length-diameter ratio and macromolecular material, improve the mechanical property of wollastonite fibre；Meanwhile, production technology is simple, constant product quality, and production cost is relatively low.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Silane coupler of the present invention is that Guangzhou Zhong Jie Chemical Industry Science Co., Ltd produces；
Titanate coupling agent of the present invention is that Guangzhou Zhong Jie Chemical Industry Science Co., Ltd produces；
Amidic-salt of the present invention is that Renqiu City De Li petroleum assistant company limited produces；
Isocyanates of the present invention is that Yantai extensively produces along chemicals company limited；
Tripolycyanamide cyanate of the present invention is that Hunan rich formed material Development Co., Ltd produces；
Wollastonite with high length-diameter ratio sample ore of the present invention is the concentrate after the wollastonite natural ore selecting and purchasing of Southern Part of Anhui Province area；
Embodiment 1
The preparation of pretreating agent:
It is previously added 100 weight parts waters the most in a kettle., 15 weight portion dimethyl sulfoxides, 5 weight portion hydrazines, 3 parts by weight acetic acid potassium, 6 parts by weight acetic acid ammoniums, 9 weight portion ammonium chloride are added in reactor by several times, mixing speed is 30 revs/min, it is warming up to 50 degrees Celsius, it is incubated 0.5 hour, can be prepared by pretreating agent；
Sample ore is pulverized, obtains primary product, and primary product is sieved, obtained the wollastonite sub-quality products that particle diameter is 15-50 mesh；
The pretreatment of wollastonite with high length-diameter ratio fiber:
It is that 15 50 mesh wollastonite with high length-diameter ratio sub-quality products stir 3 hours in 45 DEG C by weight 1:4 with the pretreating agent prepared by the 100 weight portion particle diameters produced, obtains suspension；Suspension is filtered, reclaims pretreating agent；Masterbatch after filtering is put in vacuum drying oven and is dried 3 hours in 45 DEG C, obtains pretreated wollastonite with high length-diameter ratio after crushing, sieving；
The modification of wollastonite with high length-diameter ratio fiber:
Pretreated wollastonite with high length-diameter ratio is mixed in the water of 100 weight portions, stirs for 100:1.5 with silane coupler in mass ratio, is warming up to 45 DEG C after adding diethylamine catalyst and stirs 1 hour, complete the modification of wollastonite with high length-diameter ratio；Again by the modified wollastonite with high length-diameter ratio obtained through desolventizing, dry, crush, sieve after, be 120-600 mesh by particle diameter, carry out classification according to GB/T 1345-2005 standard；Through analytical control, qualified after pack warehouse-in, obtained finished product.
Embodiment 2:
The preparation of pretreating agent:
It is previously added 100 weight parts waters the most in a kettle., 12 weight portion dimethyl sulfoxides, 3 weight portion hydrazines, 2 parts by weight acetic acid sodium, 1 parts by weight acetic acid ammonium, 2 weight portion ammonium chloride are added in reactor by several times, mixing speed is 45 revs/min, it is warming up to 48 degrees Celsius, it is incubated 0.6 hour, can be prepared by pretreating agent；
Sample ore is pulverized, obtains primary product, and primary product is sieved, obtained the wollastonite sub-quality products that particle diameter is 15-50 mesh；
The pretreatment of wollastonite with high length-diameter ratio fiber:
It is that 15 50 mesh wollastonite with high length-diameter ratio sub-quality products stir 3 hours in 48 DEG C by weight 1:3 with pretreating agent by the 100 weight portion particle diameters produced, obtains suspension；Suspension is filtered, reclaims pretreating agent, obtain masterbatch；Masterbatch after filtering is put in vacuum drying oven and is dried 10 hours in 48 DEG C, obtains pretreated wollastonite with high length-diameter ratio after crushing, sieving；
The modification of wollastonite with high length-diameter ratio fiber:
Pretreated wollastonite with high length-diameter ratio is mixed in the water of 100 weight portions, stirs for 100:1.2 with titanate coupling agent in mass ratio, is warming up to 48 DEG C after adding diethylamine catalyst and stirs 2 hours, complete the modification of wollastonite with high length-diameter ratio；Again by the modified wollastonite with high length-diameter ratio obtained through desolventizing, dry, crush, sieve after, be 120-600 mesh by particle diameter, carry out classification according to GB/T 1345-2005 standard；Through analytical control, qualified after pack warehouse-in, obtained finished product.
Embodiment 3:
Preparing of pretreating agent is same as in Example 2, in the pretreatment of wollastonite with high length-diameter ratio fiber, suspension after filtering is put in vacuum drying oven and is dried 20 hours in 60 DEG C, obtains pretreated wollastonite with high length-diameter ratio after crushing, sieving, and remaining is same as in Example 2；
In the modification of wollastonite with high length-diameter ratio fiber, wollastonite with high length-diameter ratio fiber after the pre-treatment adds amidic-salt modifying agent, amidic-salt modifying agent is 1.3:100 with the weight ratio of wollastonite sub-quality products, catalyst choice triethylene diamine, diethylamine mixture, and after adding catalyst, it being warming up to 60 DEG C of stirrings 3 hours, remaining is same as in Example 2.
Embodiment 4:
Preparing of pretreating agent is same as in Example 2, in the pretreatment of wollastonite with high length-diameter ratio fiber, suspension after filtering is put in vacuum drying oven and is dried 30 hours in 70 DEG C, obtains pretreated wollastonite with high length-diameter ratio after crushing, sieving, and remaining is same as in Example 2；
In the modification of wollastonite with high length-diameter ratio fiber, wollastonite with high length-diameter ratio fiber after the pre-treatment adds isocyanate-modified dose, isocyanate-modified dose is 1.4:100 with the weight ratio of wollastonite sub-quality products, catalyst choice stannous octoate, dibutyl tin laurate mixture, and after adding catalyst, it being warming up to 48 DEG C of stirrings 4 hours, remaining is same as in Example 2.
Embodiment 5:
Preparing of pretreating agent is same as in Example 2, in the pretreatment of wollastonite with high length-diameter ratio fiber, suspension after filtering is put in vacuum drying oven and is dried 45 hours in 80 DEG C, obtains pretreated wollastonite with high length-diameter ratio after crushing, sieving, and remaining is same as in Example 2；
In the modification of wollastonite with high length-diameter ratio fiber, wollastonite with high length-diameter ratio fiber after the pre-treatment adds tripolycyanamide cyanate, titanate coupling agent mixture modification agent, tripolycyanamide cyanate, titanate coupling agent mixture modification agent are 1:100 with the weight ratio of wollastonite sub-quality products, catalyst choice diethylamine, stannous octoate mixture, and after adding catalyst, it being warming up to 48 DEG C of stirrings 5 hours, remaining is same as in Example 2.
The present invention measures its whiteness by GB GB/T5950, and remaining index measures according to JCT-535-2007.
The technical specification of embodiment 2-5 is as follows;
As seen from the table, the whiteness of modified wollastonite with high length-diameter ratio fiber prepared by the employing present invention relatively contrasts and is significantly improved, and draw ratio is enhanced.
Modified wollastonite with high length-diameter ratio fiber embodiment 2 produced adds in PVC profile, and more general wollastonite is better, and loading is 6%.
Claims (4)
1. modified wollastonite with high length-diameter ratio fiber and preparation method thereof, it is characterised in that include wollastonite with high length-diameter ratio preparation section A, wollastonite with high length-diameter ratio pretreatment process B, wollastonite with high length-diameter ratio modified process C；
Wollastonite with high length-diameter ratio preparation section A comprises the following steps:
Sample ore is pulverized by step (1), obtains primary product；
Primary product is sieved by step (2), has obtained the wollastonite sub-quality products that particle diameter is 15-50 mesh；
Wollastonite with high length-diameter ratio pretreatment process B comprises the following steps:
The particle diameter that wollastonite with high length-diameter ratio preparation section A obtains is that 15 50 mesh sub-quality products stir 3 40 hours in 35 90 DEG C for 1:3 1:20 in mass ratio with pretreating agent by step (1), obtains suspension；
The suspension that step (1) described in wollastonite with high length-diameter ratio preparation section B obtains is filtered and reclaims pretreating agent by step (2)；
Suspension after step (2) filtration described in wollastonite with high length-diameter ratio preparation section B is put in vacuum drying oven and is dried 2 45 hours in 40 80 DEG C by step (3), obtains pretreated wollastonite with high length-diameter ratio after crushing, sieving；
Wollastonite with high length-diameter ratio modified process C comprises the following steps:
The pretreated wollastonite with high length-diameter ratio that step (3) described in wollastonite with high length-diameter ratio preparation section B obtains is mixed in the solvent of 100 weight portions, stirs for 100:1 100:15 with modifying agent by step (1) in mass ratio, it is warming up to 35 60 DEG C after adding catalyst stir 15 hours, completes the modification of wollastonite with high length-diameter ratio；
The modified wollastonite with high length-diameter ratio that step (1) described in wollastonite with high length-diameter ratio preparation section C is obtained by step (2) through desolventizing, dry, crush, sieve after, be 120-600 mesh by particle diameter, carry out classification according to GB/T 1345-2005 standard；
Step (3) the modified wollastonite with high length-diameter ratio that step (2) described in wollastonite with high length-diameter ratio preparation section C obtains is analyzed inspection, qualified after pack warehouse-in, obtained finished product.
A kind of modified wollastonite with high length-diameter ratio the most according to claim 1 and preparation method thereof, it is characterised in that: described pretreating agent is the mixture of one or more in dimethyl sulfoxide, hydrazine, potassium acetate, sodium acetate, ammonium acetate, ammonium chloride.
A kind of modified wollastonite with high length-diameter ratio the most according to claim 1 and preparation method thereof, it is characterised in that described modifying agent is the mixture of one or more in silane coupler, titanate coupling agent, amidic-salt, isocyanates, tripolycyanamide cyanate.
A kind of modified wollastonite with high length-diameter ratio the most according to claim 1 and preparation method thereof, it is characterised in that described catalyst is the mixture of one or more in triethylene diamine, diethylamine, stannous octoate, dibutyl tin laurate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107724166A (en) * | 2017-10-19 | 2018-02-23 | 蒋文明 | A kind of preparation method of modified grammite |
| CN111005222A (en) * | 2019-12-12 | 2020-04-14 | 湖北冯家山硅纤有限公司 | Surface treatment method of superfine and overlong silicon fiber |
| CN111247224A (en) * | 2017-10-26 | 2020-06-05 | 日立化成株式会社 | Friction member, friction material composition for underlayer material, and friction material |
| CN111909423A (en) * | 2020-08-20 | 2020-11-10 | 湖北冯家山硅纤有限公司 | Wollastonite fiber suitable for nylon products and preparation method thereof |
| CN111925218A (en) * | 2020-07-22 | 2020-11-13 | 江西广源化工有限责任公司 | Modified wollastonite and preparation method and application thereof |
| CN112441592A (en) * | 2019-08-28 | 2021-03-05 | 西南科技大学 | Controllable preparation method of high-purity wollastonite fiber |
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| JPH0716865A (en) * | 1993-07-06 | 1995-01-20 | Sumitomo Bayer Urethane Kk | Reinforced rim molded product |
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| JPH0716865A (en) * | 1993-07-06 | 1995-01-20 | Sumitomo Bayer Urethane Kk | Reinforced rim molded product |
| CN102249530A (en) * | 2011-04-22 | 2011-11-23 | 安徽绿能技术研究院 | Wollastonite fiber with large length-diameter ratio and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107724166A (en) * | 2017-10-19 | 2018-02-23 | 蒋文明 | A kind of preparation method of modified grammite |
| CN111247224A (en) * | 2017-10-26 | 2020-06-05 | 日立化成株式会社 | Friction member, friction material composition for underlayer material, and friction material |
| CN112441592A (en) * | 2019-08-28 | 2021-03-05 | 西南科技大学 | Controllable preparation method of high-purity wollastonite fiber |
| CN111005222A (en) * | 2019-12-12 | 2020-04-14 | 湖北冯家山硅纤有限公司 | Surface treatment method of superfine and overlong silicon fiber |
| CN111005222B (en) * | 2019-12-12 | 2022-09-13 | 湖北冯家山硅纤有限公司 | Surface treatment method of superfine and overlong silicon fiber |
| CN111925218A (en) * | 2020-07-22 | 2020-11-13 | 江西广源化工有限责任公司 | Modified wollastonite and preparation method and application thereof |
| CN111909423A (en) * | 2020-08-20 | 2020-11-10 | 湖北冯家山硅纤有限公司 | Wollastonite fiber suitable for nylon products and preparation method thereof |
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| CN105819678B (en) | 2017-12-29 |
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