CN115849425A - Preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive - Google Patents
Preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive Download PDFInfo
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- CN115849425A CN115849425A CN202211585989.8A CN202211585989A CN115849425A CN 115849425 A CN115849425 A CN 115849425A CN 202211585989 A CN202211585989 A CN 202211585989A CN 115849425 A CN115849425 A CN 115849425A
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- calcium carbonate
- nano calcium
- low
- silicone adhesive
- modulus high
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 88
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 44
- 239000013464 silicone adhesive Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 26
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 18
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 18
- 239000004571 lime Substances 0.000 claims abstract description 18
- -1 long-chain fatty acid sodium salt Chemical class 0.000 claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 239000000292 calcium oxide Substances 0.000 claims abstract description 10
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000011265 semifinished product Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 239000004519 grease Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 6
- 239000008399 tap water Substances 0.000 claims abstract description 6
- 235000020679 tap water Nutrition 0.000 claims abstract description 6
- 235000019738 Limestone Nutrition 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000006028 limestone Substances 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019482 Palm oil Nutrition 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000003240 coconut oil Substances 0.000 claims description 3
- 235000019864 coconut oil Nutrition 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000002540 palm oil Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 2
- CVYDEWKUJFCYJO-UHFFFAOYSA-M sodium;docosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O CVYDEWKUJFCYJO-UHFFFAOYSA-M 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000000945 filler Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
The invention relates to the technical field of preparation of nano calcium carbonate, and discloses a preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive, which comprises the following steps: calcining limestone at 1100-1200 ℃ to prepare quicklime; stirring and digesting quicklime and tap water to prepare lime slurry; transferring the lime slurry to a carbonization tower for cooling, adding a crystal form control agent into the lime slurry, and introducing carbon dioxide for carbonation reaction to obtain a calcium carbonate suspension with the pH value of 7.5; transferring the calcium carbonate suspension into a treatment barrel, heating, adding long-chain fatty acid sodium salt for surface modification to obtain finished slurry; respectively carrying out filter pressing dehydration, drying dehydration and crushing on the finished product slurry to obtain semi-finished product powder; and adding grease into the semi-finished product powder for dry modification to obtain the active nano calcium carbonate. The preparation method is suitable for preparing the nano calcium carbonate for the low-modulus high-elasticity silicone adhesive, and has the advantages of low modulus, high elastic recovery rate, good thixotropy and good fluidity.
Description
Technical Field
The invention relates to the technical field of preparation of nano calcium carbonate, in particular to a preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive.
Background
The organosilicon sealant, called silicone adhesive for short, is mainly composed of hydroxy-terminated polydimethylsiloxane (107 adhesive), filler, cross-linking agent, catalyst and other raw materials. At present, according to the market demand, the performance of silicone adhesive is continuously developing towards low modulus and high elastic recovery rate. In the raw material composition of the silicone adhesive, the filler is a main factor influencing the modulus and elastic recovery rate of the silicone adhesive. And nano calcium carbonate is the most commonly used silicone adhesive filler with the largest amount. Therefore, it is required to prepare an active nano calcium carbonate which can endow the silicone adhesive with low modulus and high elastic recovery rate.
Disclosure of Invention
The invention provides a preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive, which solves the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive comprises the following steps:
1) Calcining limestone at 1100-1200 ℃ to prepare quicklime;
2) Stirring and digesting quicklime and tap water to prepare lime slurry;
3) Transferring the lime slurry to a carbonization tower for cooling, adding a crystal form control agent into the lime slurry, and introducing carbon dioxide for carbonation reaction to obtain a calcium carbonate suspension with the pH value of 7.5;
4) Transferring the calcium carbonate suspension into a treatment barrel, heating, adding long-chain fatty acid sodium salt for surface modification to obtain finished slurry;
5) Respectively carrying out filter pressing dehydration, drying dehydration and crushing on the finished product slurry to obtain semi-finished product powder;
6) And adding grease into the semi-finished product powder for dry modification to obtain the active nano calcium carbonate.
As a preferred technical scheme of the invention, in the step 2), the mass ratio of the quicklime to the tap water is 2.
As a preferable embodiment of the present invention, in the step 2), the specific gravity of the lime slurry is 1.060.
As a preferable technical scheme of the invention, in the step 2), the temperature of the lime slurry is reduced to 25-30 ℃ in a carbonization tower.
As a preferable technical scheme of the invention, in the step 3), the crystal form control agent is prepared by compounding oxalate and sucrose, the compounding ratio is 1-3, and the addition amount of the crystal form control agent is 0.01-0.03% of the mass of the lime slurry.
In a preferred embodiment of the present invention, in the step 3), the volume concentration of the carbon dioxide is 30 to 33%.
As a preferred technical solution of the present invention, in step 4), the calcium carbonate suspension is heated to 80-90 ℃ in a treatment barrel.
As a preferable technical scheme of the invention, in the step 4), the long-chain fatty acid sodium salt is fatty acid sodium salt such as sodium eicosatedate, sodium docosate and sodium docetanate, and the addition amount of the long-chain fatty acid sodium salt is 3.5-5.0% of the dry basis of calcium carbonate.
As a preferable technical solution of the present invention, in the step 4), the oil and fat is oil and fat such as palm oil, coconut oil, and the like.
As a preferred embodiment of the present invention.
The invention has the following advantages:
1. the crystal form control agent is adopted for carbonation reaction, so that the shape of the nano calcium carbonate is more regular, and the nano calcium carbonate filled silicone adhesive is endowed with lower modulus and more excellent fluidity;
2. the long-chain fatty acid sodium salt is adopted for wet modification, compared with stearic acid, the main chain is longer, the winding performance among molecules is better, and the nano calcium carbonate filled silicone adhesive can be endowed with higher elastic recovery rate;
3. the grease is adopted for secondary dry modification, and the characteristics of the grease are utilized, so that the nano calcium carbonate filled silicone adhesive is endowed with lower modulus, and the thixotropy can be improved.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In one embodiment, a method for preparing nano calcium carbonate for low-modulus high-elasticity silicone adhesive comprises the following steps:
1) Calcining limestone at 1100-1200 ℃ to prepare quicklime;
2) Stirring and digesting quicklime and tap water according to a mass ratio of 2;
3) Moving the lime slurry to a carbonization tower, cooling the lime slurry to 25-30 ℃, adding a crystal form control agent (oxalate and sucrose are compounded, the compounding ratio is 1-3), the adding amount is 0.01-0.03% of the mass of the lime slurry, then introducing carbon dioxide (the volume concentration is 30-33%) for carbonation reaction, and stopping the reaction until the pH of a reaction system is 7.5 to obtain a calcium carbonate suspension;
4) Transferring the calcium carbonate suspension to a treatment barrel, heating the suspension to 80-90 ℃, adding long-chain fatty acid sodium salt (fatty acid sodium salts such as sodium eicosatedate, sodium docosate and sodium docecanoate) for surface modification, wherein the addition amount is 3.5-5.0% of the dry basis of the calcium carbonate, and performing surface modification for 30min to obtain finished product slurry;
5) Respectively carrying out filter pressing dehydration, drying dehydration and crushing on the finished product slurry to obtain semi-finished product powder;
6) Adding oil (such as palm oil, coconut oil, etc.) into the semi-finished product powder, and performing dry modification at 80-95 deg.C, wherein the addition amount is 0.5-2.0% of calcium carbonate dry basis, to obtain active nano calcium carbonate.
The invention is suitable for a preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive, and the nano carbonic acid prepared by the method
The calcium is filled in the silicone adhesive, and has the advantages of low modulus, high elastic recovery rate, good thixotropy and good fluidity.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive is characterized by comprising the following steps:
1) Calcining limestone at 1100-1200 ℃ to prepare quicklime;
2) Stirring and digesting quicklime and tap water to prepare lime slurry;
3) Transferring the lime slurry to a carbonization tower for cooling, adding a crystal form control agent into the lime slurry, and introducing carbon dioxide for carbonation reaction to obtain a calcium carbonate suspension with the pH value of 7.5;
4) Transferring the calcium carbonate suspension into a treatment barrel, heating, and adding long-chain fatty acid sodium salt for surface modification to obtain finished product slurry;
5) Respectively carrying out filter pressing dehydration, drying dehydration and crushing on the finished product slurry to obtain semi-finished product powder;
6) And adding grease into the semi-finished product powder for dry modification to obtain the active nano calcium carbonate.
2. The method for preparing nano calcium carbonate for the low-modulus high-elasticity silicone adhesive according to claim 1, wherein in the step 2), the mass ratio of the quicklime to the tap water is 2.
3. The method for preparing nano calcium carbonate for the low-modulus high-elasticity silicone adhesive according to claim 1, wherein in the step 2), the specific gravity of the lime slurry is 1.060.
4. The method for preparing nano calcium carbonate for the low-modulus high-elasticity silicone adhesive according to claim 1, wherein in the step 2), the temperature of the lime slurry is reduced to 25-30 ℃ in a carbonization tower.
5. The preparation method of the nano calcium carbonate for the low-modulus high-elasticity silicone adhesive according to claim 1, characterized in that in step 3), the crystal form control agent is prepared by compounding oxalate and sucrose, the compounding ratio is 1-3, and the addition amount of the crystal form control agent is 0.01-0.03% of the mass of the lime slurry.
6. The method for preparing nano calcium carbonate for the low-modulus high-elasticity silicone adhesive according to claim 1, wherein in the step 3), the volume concentration of the carbon dioxide is 30-33%.
7. The method for preparing nano calcium carbonate for the low-modulus high-elasticity silicone adhesive according to claim 1, wherein in the step 4), the calcium carbonate suspension is heated to 80-90 ℃ in a treatment barrel.
8. The method for preparing nano calcium carbonate for the low-modulus high-elasticity silicone adhesive according to claim 1, wherein in the step 4), the long-chain fatty acid sodium salt is fatty acid sodium salt such as sodium eicosatedate, sodium docosanate and sodium docetradecanoate, and the addition amount of the long-chain fatty acid sodium salt is 3.5-5.0% of the dry basis of calcium carbonate.
9. The method for preparing nano calcium carbonate for the low-modulus high-elasticity silicone adhesive according to claim 1, wherein in the step 6), the grease is palm oil, coconut oil and the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211585989.8A CN115849425A (en) | 2022-12-09 | 2022-12-09 | Preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211585989.8A CN115849425A (en) | 2022-12-09 | 2022-12-09 | Preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive |
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| Publication Number | Publication Date |
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| CN115849425A true CN115849425A (en) | 2023-03-28 |
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| CN202211585989.8A Pending CN115849425A (en) | 2022-12-09 | 2022-12-09 | Preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475759A (en) * | 2009-01-21 | 2009-07-08 | 山东海泽纳米材料有限公司 | Practical method for preparing high thixotropy surface treating nano calcium carbonate |
| CN101570342A (en) * | 2009-06-11 | 2009-11-04 | 福建省万旗非金属材料有限公司 | Method for preparing high-whiteness nanometer calcium carbonate special for silicone sealant by utilizing low-grade limestone by wet method |
| JP2011094134A (en) * | 2009-10-02 | 2011-05-12 | Maruo Calcium Co Ltd | Surface-treated calcium carbonate filler for two-liquid type curable resin composition, and two-liquid type curable resin composition prepared by blending the filler |
| CN105400237A (en) * | 2015-12-17 | 2016-03-16 | 广西华纳新材料科技有限公司 | Surface treatment method for nanometer calcium carbonate applied to fill silicone sealant |
| CN106675109A (en) * | 2016-11-11 | 2017-05-17 | 恩平燕怡新材料有限公司 | Preparation method of high-activity nano calcium carbonate subjected to surface bioactive treatment |
| CN111003722A (en) * | 2019-08-28 | 2020-04-14 | 安徽省宣城市华纳新材料科技有限公司 | Preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive |
-
2022
- 2022-12-09 CN CN202211585989.8A patent/CN115849425A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475759A (en) * | 2009-01-21 | 2009-07-08 | 山东海泽纳米材料有限公司 | Practical method for preparing high thixotropy surface treating nano calcium carbonate |
| CN101570342A (en) * | 2009-06-11 | 2009-11-04 | 福建省万旗非金属材料有限公司 | Method for preparing high-whiteness nanometer calcium carbonate special for silicone sealant by utilizing low-grade limestone by wet method |
| JP2011094134A (en) * | 2009-10-02 | 2011-05-12 | Maruo Calcium Co Ltd | Surface-treated calcium carbonate filler for two-liquid type curable resin composition, and two-liquid type curable resin composition prepared by blending the filler |
| CN105400237A (en) * | 2015-12-17 | 2016-03-16 | 广西华纳新材料科技有限公司 | Surface treatment method for nanometer calcium carbonate applied to fill silicone sealant |
| CN106675109A (en) * | 2016-11-11 | 2017-05-17 | 恩平燕怡新材料有限公司 | Preparation method of high-activity nano calcium carbonate subjected to surface bioactive treatment |
| CN111003722A (en) * | 2019-08-28 | 2020-04-14 | 安徽省宣城市华纳新材料科技有限公司 | Preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive |
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