CN102070662A - Preparation method of fluorine-silicon surfactant - Google Patents
Preparation method of fluorine-silicon surfactant Download PDFInfo
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- CN102070662A CN102070662A CN201010604955.XA CN201010604955A CN102070662A CN 102070662 A CN102070662 A CN 102070662A CN 201010604955 A CN201010604955 A CN 201010604955A CN 102070662 A CN102070662 A CN 102070662A
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- silicon surfactant
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- fluorine
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 21
- 239000013067 intermediate product Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 30
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- IEPMHPLKKUKRSX-UHFFFAOYSA-J silicon(4+);tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Si+4] IEPMHPLKKUKRSX-UHFFFAOYSA-J 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- JMUMVYONCABRHT-UHFFFAOYSA-N [Pt].Cl(=O)(=O)(=O)O Chemical compound [Pt].Cl(=O)(=O)(=O)O JMUMVYONCABRHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 9
- 239000002689 soil Substances 0.000 abstract description 9
- 238000002834 transmittance Methods 0.000 abstract description 8
- 239000005052 trichlorosilane Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- -1 alkyl ethyl iodide Chemical compound 0.000 abstract description 5
- 239000003921 oil Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 abstract description 2
- 238000004886 process control Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 125000005192 alkyl ethylene group Chemical group 0.000 abstract 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000010792 warming Methods 0.000 description 11
- 230000003666 anti-fingerprint Effects 0.000 description 8
- HDEPFLVKWKPGFZ-UHFFFAOYSA-N Cl(=O)(=O)O.[Pt] Chemical compound Cl(=O)(=O)O.[Pt] HDEPFLVKWKPGFZ-UHFFFAOYSA-N 0.000 description 7
- 241000209094 Oryza Species 0.000 description 7
- 235000007164 Oryza sativa Nutrition 0.000 description 7
- 235000009566 rice Nutrition 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002912 waste gas Substances 0.000 description 6
- 239000004519 grease Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YCBPKOZNGFQMPB-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-hexadecafluorooct-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YCBPKOZNGFQMPB-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- AUNKHUQNKUEUJA-UHFFFAOYSA-N 2-iodododecane Chemical compound CCCCCCCCCCC(C)I AUNKHUQNKUEUJA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
Abstract
The invention discloses a preparation method of a fluorine-silicon surfactant. The method comprises the following steps of: continually dripping 13 to 18 weight parts of trichlorosilane into 44 to 65 weight parts of perfluor alkyl ethylene or perfluor alkyl ethyl iodide serving as a raw material in the presence of 0.1 to 1.0 weight part of noble metal catalyst so as to obtain an intermediate product; and adding 14.8 to 20 weight parts of high-boiling-point solvent into the intermediate product, continuously dripping 10 to 16.35 weight parts of methanol or ethanol for reacting, decompressing and rectifying so as to obtain a target product. In the method, raw materials are readily available, byproduct is not produced, a reaction in an entire synthesis process is stable, process control is stable, safety, low cost and easy separation are realized, the yield of a final fluorine-silicon surfactant is over 95 percent, and the purity of the surfactant is over 98 percent. Due to the presence of a siloxane active group, the fluorine-silicon surfactant can react with and be tightly combined with substances with a hydroxy functional group, such as glass and the like, so that the surface of the fluorine-silicon surfactant has high waterproofness, oil resistance and soil resistance, surface tension is less than 17.6 dynes per meter, and light transmittance is over 99.9 percent.
Description
Technical field
The present invention relates to a kind of preparation method of fluoride silicon surfactant.
Background technology
Tensio-active agent is widely used in glass industry, automobile industry, electronics, special surface process field, requires to have excellent waterproof, grease proofing and rustless property, and good anti-fingerprint characteristic, anti-soil, resistance to fogging energy.Existing tensio-active agent mainly contains hydrocarbon and fluorochemical surfactant.The hc-surfactant surface energy is big, does not have waterproof, oil preventing performance.The fluorochemical surfactant surface energy is little, has waterproof, oil preventing performance, but the production cost height is poorly soluble, and Application Areas is restricted.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of have excellent waterproof, grease proofing, antifog and antirust, anti-soil and anti-fingerprint performance, and production cost is low, the preparation method of the fluoride silicon surfactant of applied range.
Technical solution of the present invention is:
A kind of preparation method of fluoride silicon surfactant, it is characterized in that: is raw material according to the parts by weight meter with 44～65 parts of perfluoro alkyl ethylenes or perfluor alkyl ethide iodine, in the presence of 0.1～1.0 part of noble metal catalyst, drip 13～18 parts of trichlorosilanes continuously and react, 1～5 hour reaction times obtained intermediate product; 14.8～20 parts of high boiling solvents are added in the intermediate product, drip 10～16.35 parts of methyl alcohol or ethanol then continuously, the reaction times is 1～5 hour, and whole reaction process temperature is controlled under 40～120 ℃, and rectification under vacuum makes target product.
Above-mentioned perfluoro alkyl ethylene has F(CF
2) nCH
2=CH
2Structure, perfluor alkyl ethide iodine tool F (CF
2)
nCH
2CH
2The I structure, wherein n is 6～12 even number.
Above-mentioned high boiling solvent is dimethylbenzene or pyridine.
Above-mentioned noble metal catalyst is one or both a mixture of perchloric acid platinum and Palladous chloride.
The preparation method of above-mentioned fluoride silicon surfactant, temperature of reaction are 80～90 ℃, 2～3 hours reaction times.
It is raw material that the present invention adopts perfluoro alkyl ethylene or perfluor alkyl ethide iodine, and raw material is easy to get, and does not produce by product, adopt the process control that drips continuously, the entire synthesis process reacting balance, technology controlling and process is stable, safe, inexpensive, separate simple, final obtain have a F (CF
2) nCH
2CH
2Si(OR
3) fluoride silicon surfactant (R is methyl or ethyl in the structural formula, and n is 6,8,10,12 even number) of structure, yield is greater than 95%, and purity can reach more than 98%.In this fluoride silicon surfactant because of containing the siloxanes active group, can the substance reaction of hydroxy functional group be arranged and mortise with glass etc., thereby make its surface have excellent waterproof, grease proofing and antifouling property, and having lower surface tension (surface tension is less than 17.6 dyne/rice), transmittance is up to 99.9% simultaneously.
Embodiment
Embodiment 1
Agitator is being housed, prolong, thermometer, addition funnel, add perfluoro capryl ethene 446.1g in the 1000ml four-hole boiling flask of nitrogen conduit, add 0.5g chloric acid platinum, stirring is warming up to 40 ℃, begin to drip trichlorosilane 136g after temperature is steady, the dropping time is 1h, continue reaction 2h, separate, filter the back and obtain intermediate product 570g, in intermediate product, add pyridine 150g and be warming up to 80 ℃, treat to begin to drip methyl alcohol 100g after temperature steadily, dropwise in the 1h, dropwise the back and continue reaction 2h, the 10%NaOH solution absorption of the waste gas in the reaction process obtains target product 550g with the product that obtains after rectification under vacuum removes pyridine, yield 97%, purity 99%.Handle the back glass surface through surface tension 17.5 dyne/rice with this product, have good anti-soil, anti-fingerprint performance, transmittance is 99.98%.
Embodiment 2
In being housed, the 1000ml four-hole boiling flask of agitator, prolong, thermometer, addition funnel, nitrogen conduit adds perfluoro hexyl ethene 450g, add 1.0g chloric acid platinum, stirring is warming up to 50 ℃, begin to drip trichlorosilane 180g after temperature is steady, the dropping time is 1h, continue reaction 3h, separate, filter the back and obtain intermediate product 613g.In intermediate product, add pyridine 200g and be warming up to 90 ℃, treat to begin to drip methyl alcohol 110g after temperature steadily, 0.5h in dropwise, dropwise the back and continue reaction 0.5h, waste gas in reaction process 10%NaOH solution absorption, the product that obtains after removing pyridine, is obtained target product 590g, yield 97.2%, purity 98% in rectification under vacuum.The glass surface of handling with this product has good anti-soil, anti-fingerprint performance through surface tension 17 dyne/rice, and transmittance is 99.9%.
Embodiment 3
Agitator is being housed, prolong, thermometer, addition funnel, add perfluoro capryl ethene 500g in the 1000ml four-hole boiling flask of nitrogen conduit, add 0.5g chloric acid platinum, stirring is warming up to 100 ℃, begin to drip trichlorosilane 160g after temperature is steady, the dropping time is 1h, continue reaction 1h, separate, filter the back and obtain intermediate product 620g, add pyridine 180g and be warming up to 120 ℃, treat to begin to drip ethanol 160g after temperature steadily, dropwise in the 1h, dropwise the back and continue reaction 3h, the 10%NaOH solution absorption of the waste gas in the reaction process obtains target product 661g with the product that obtains after rectification under vacuum removes the solvent pyridine, yield 97%, purity 98.5%.The glass surface of handling with this product has good anti-soil, anti-fingerprint performance through surface tension 16.5 dyne/rice, and transmittance is 99.95%.
Embodiment 4
Agitator is being housed, prolong, thermometer, addition funnel, add perfluoro capryl iodoethane 600g in the 1000ml four-hole boiling flask of nitrogen conduit, add 0.9g chloric acid platinum, stirring is warming up to 90 ℃, begin to drip trichlorosilane 160g after temperature is steady, the dropping time is 0.5h, continue reaction 0.5h, separate, filter the back and obtain intermediate product 620g, add pyridine 160g and be cooled to 40 ℃, treat to begin to drip ethanol 163g after temperature steadily, dropwise in the 1h, dropwise the back and continue reaction 1h, the 10%NaOH solution absorption of the waste gas in the reaction process obtains target product 652g with the product that obtains after rectification under vacuum removes the solvent pyridine, yield 96%, purity 98%.The glass surface of handling with this product has good anti-soil, anti-fingerprint performance through surface tension 16.8 dyne/rice, and the while transmittance can reach 99.96%.
Embodiment 5
Agitator is being housed, prolong, thermometer, addition funnel, add perfluor decyl ethylene 564g in the 1000ml four-hole boiling flask of nitrogen conduit, add the 0.4g Palladous chloride, stirring is warming up to 120 ℃, begin to drip trichlorosilane 140g after temperature is steady, the dropping time is 1h, continue reaction 3h, separate, filter the back and obtain intermediate product 640g, add pyridine 150g and be warming up to 100 ℃, treat to begin to drip methyl alcohol 110g after temperature steadily, in 1h, dropwise, dropwise the back and continue reaction 4h, the 10%NaOH solution absorption of the waste gas in the reaction process obtains target product 660g with the product that obtains after rectification under vacuum removes the solvent pyridine, yield 95.6%, purity 98.2%.The glass surface of handling with this product has good anti-soil, anti-fingerprint performance through surface tension 17 dyne/rice, and transmittance is 99.98%.
Embodiment 6
Agitator is being housed, prolong, thermometer, addition funnel, add perfluor decyl iodoethane 654g in the 1000ml four-hole boiling flask of nitrogen conduit, add the 0.2g Palladous chloride, stirring is warming up to 80 ℃, begin to drip trichlorosilane 145g after temperature is steady, the dropping time is 1h, continue reaction 4h, separate, filter the back and obtain intermediate product 640g, add pyridine 148g and be warming up to 70 ℃, treat to begin to drip methyl alcohol 116g after temperature steadily, 1h dropwises, dropwise the back and continue reaction 2h, the 10%NaOH solution absorption of the waste gas in the reaction process obtains target product 650g with the product that obtains after rectification under vacuum removes the solvent pyridine, yield 95%, purity 99.2%.The glass surface of handling with this product has good anti-soil, anti-fingerprint performance through surface tension 17.2 dyne/rice, and transmittance is 99.92%.
Embodiment 7
Catalyzer adopts chloric acid platinum and Palladous chloride to mix, and chloric acid platinum and Palladous chloride blending ratio are not limit, chloric acid platinum 0.1g, Palladous chloride 0.2g in this example, and reaction conditions and reaction process are with embodiment 1-embodiment 6.
Pyridine replaces with dimethylbenzene in the foregoing description, and reaction conditions and reaction process are with embodiment 1-embodiment 7.
Claims (5)
1. the preparation method of a fluoride silicon surfactant, it is characterized in that: is raw material according to the parts by weight meter with 44～65 parts of perfluoro alkyl ethylenes or perfluor alkyl ethide iodine, in the presence of 0.1～1.0 part of noble metal catalyst, drip 13～18 parts of trichlorosilanes continuously and react, 1～5 hour reaction times obtained intermediate product; 14.8～20 parts of high boiling solvents are added in the intermediate product, drip 10～16.35 parts of methyl alcohol or ethanol then continuously, the reaction times is 1～5 hour, and whole reaction process temperature is controlled under 40～120 ℃, and rectification under vacuum makes target product.
2. the preparation method of fluoride silicon surfactant according to claim 1, it is characterized in that: perfluoro alkyl ethylene has F(CF
2) nCH
2=CH
2Structure, perfluor alkyl ethide iodine tool F (CF
2)
nCH
2CH
2The I structure, wherein n is 6～12 even number.
3. the preparation method of fluoride silicon surfactant according to claim 1, it is characterized in that: described high boiling solvent is dimethylbenzene or pyridine.
4. the preparation method of fluoride silicon surfactant according to claim 1 is characterized in that: noble metal catalyst is one or both a mixture of perchloric acid platinum and Palladous chloride.
5. the preparation method of fluoride silicon surfactant according to claim 1, it is characterized in that: temperature of reaction is 80～90 ℃, 2～3 hours reaction times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010604955A CN102070662B (en) | 2010-12-25 | 2010-12-25 | Preparation method of fluorine-silicon surfactant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010604955A CN102070662B (en) | 2010-12-25 | 2010-12-25 | Preparation method of fluorine-silicon surfactant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102070662A true CN102070662A (en) | 2011-05-25 |
| CN102070662B CN102070662B (en) | 2012-10-10 |
Family
ID=44029439
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010604955A Active CN102070662B (en) | 2010-12-25 | 2010-12-25 | Preparation method of fluorine-silicon surfactant |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829641A (en) * | 2015-05-12 | 2015-08-12 | 傅筠 | Fluorine-containing organosilicone monomer and preparation method thereof |
| CN105801618A (en) * | 2016-05-04 | 2016-07-27 | 厦门建霖工业有限公司 | Preparation method of fluorine-containing super-hydro-oleophobic agent |
| CN106350236A (en) * | 2016-08-30 | 2017-01-25 | 申立德 | Automobile dry-cleaning fluid and preparing method thereof |
| CN106693829A (en) * | 2016-12-29 | 2017-05-24 | 柏青龙 | Modified composite type surface active agent |
| CN107602866A (en) * | 2017-08-28 | 2018-01-19 | 无锡龙驰氟硅新材料有限公司 | A kind of fluoride silicon surfactant and preparation method thereof |
| CN109810800A (en) * | 2019-02-02 | 2019-05-28 | 江苏云瀚股份有限公司 | Expelling water light self-emulsifying composition |
| CN116589910A (en) * | 2023-06-01 | 2023-08-15 | 黄山市天马科技有限公司 | High-transparency environment-friendly silane modified waterproof coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58172243A (en) * | 1982-04-02 | 1983-10-11 | Asahi Glass Co Ltd | Treating agent for glass surface |
| JPH0195181A (en) * | 1987-10-05 | 1989-04-13 | Daikin Ind Ltd | Water-and oil-repellent material composition |
-
2010
- 2010-12-25 CN CN201010604955A patent/CN102070662B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58172243A (en) * | 1982-04-02 | 1983-10-11 | Asahi Glass Co Ltd | Treating agent for glass surface |
| JPH0195181A (en) * | 1987-10-05 | 1989-04-13 | Daikin Ind Ltd | Water-and oil-repellent material composition |
Non-Patent Citations (2)
| Title |
|---|
| 《Bulletin of Chemical Society of Japan》 19931231 Norio Yoshino et al Syntheses and Reactions of Metal Organics. XVIII. Syntheses of (1H,1H,2H,2H-Polyfluoroalkyl)trimethoxysilanes and Surface Modification of Glass Plate 第1754页左栏第1段～第1758页右栏第2段 1-5 第66卷, 第6期 * |
| 《广东有色金属学报》 20041120 卜向明等 氯硅烷醇解中氯化氢的去除方法 第124页左栏第1行～第126页右栏最后一行 1-5 第14卷, 第2期 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829641A (en) * | 2015-05-12 | 2015-08-12 | 傅筠 | Fluorine-containing organosilicone monomer and preparation method thereof |
| CN104829641B (en) * | 2015-05-12 | 2018-01-19 | 傅筠 | A kind of fluorine-containing organic silicon monomer and preparation method thereof |
| CN105801618A (en) * | 2016-05-04 | 2016-07-27 | 厦门建霖工业有限公司 | Preparation method of fluorine-containing super-hydro-oleophobic agent |
| CN106350236A (en) * | 2016-08-30 | 2017-01-25 | 申立德 | Automobile dry-cleaning fluid and preparing method thereof |
| CN106693829A (en) * | 2016-12-29 | 2017-05-24 | 柏青龙 | Modified composite type surface active agent |
| CN107602866A (en) * | 2017-08-28 | 2018-01-19 | 无锡龙驰氟硅新材料有限公司 | A kind of fluoride silicon surfactant and preparation method thereof |
| CN109810800A (en) * | 2019-02-02 | 2019-05-28 | 江苏云瀚股份有限公司 | Expelling water light self-emulsifying composition |
| CN116589910A (en) * | 2023-06-01 | 2023-08-15 | 黄山市天马科技有限公司 | High-transparency environment-friendly silane modified waterproof coating |
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| Publication number | Publication date |
|---|---|
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