CN103757915A - Novel environment-friendly oil and water repellent agent for leather - Google Patents
Novel environment-friendly oil and water repellent agent for leather Download PDFInfo
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- CN103757915A CN103757915A CN201310535905.4A CN201310535905A CN103757915A CN 103757915 A CN103757915 A CN 103757915A CN 201310535905 A CN201310535905 A CN 201310535905A CN 103757915 A CN103757915 A CN 103757915A
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- repellent agent
- novel environment
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Abstract
The invention discloses a novel environment-friendly oil and water repellent agent for leather. The agent consists of the following components by weight: 4-54 parts of fluorine monomers, 3-40 parts of alkyl acrylate, 1-10 parts of non-fluorinated monomers, 0.08-1 part of an initiator and 56-152 parts of a solvent. The novel environment-friendly oil and water repellent agent for leather provided by the invention does not contain perfluorooctanoic acid compound (PFOA) or perfluorooctane sulfonic acid compounds (PFOS), which cause negative impact on the environment, and has excellent waterproof and oil-proof performances.
Description
Technical field
The present invention relates to water and oil repellent agent, be specifically related to a kind of leather novel environment friendly water and oil repellent agent.
Background technology
Fluoropolymer has unrivaled advantage at aspects such as surface-activity, waterproof, grease proofing, antifouling, heat resistance and corrosion resistances, can give the waterproof and oilproof performance that product is good, is conventional water and oil repellent agent.
The fluorine-containing part of fluoropolymer is mainly perfluoro octyl sulfonic acid (PFOS) and derivative thereof at present, because it has high persistence and cumulative bad in environment, has potential danger, thereby is subject to strict restriction in developed countries such as the U.S., European Union.PFOS substitute has become new study hotspot, take carbon number as 6 and following perfluoroalkyl or the oligomerization of hexafluoropropylene body of usining as the fluoro-containing group of fluorine-containing thing, be two kinds of effective alternative route.
When preparing composition of waterproofing and oil-proof agent, researcher's focus mainly concentrate on last alternative route (using carbon number as 6 and following perfluoroalkyl as the fluoro-containing group of fluorine-containing thing) on.
As China Patent Publication No. CN101006149A has announced a kind of composition of waterproofing and oil-proof agent, the fluorinated copolymer in composition is that to contain carbon number be 1～6 Polyfluoroalkyl or the polymerizable monomer of the rare base of polyfluoro chain.
And for example China Patent Publication No. CN102575435A has announced a kind of paper water and oil repellent agent, and wherein said fluorinated copolymer is that 1～6 perfluoroalkyl monomer, hydrophilic monomer and the monomer copolymerization with anion supply group obtain by having carbon number.
And for example China Patent Publication No. CN102634981A has announced a kind of weak cation waterproof and oilproof agent emulsion, the polymer of wherein said fluoropolymer for containing perfluoro hexyl (butyl) ethyl propylene acid esters or methacrylate.
The weak point of composition of waterproofing and oil-proof agent prepared by above-mentioned patented technology is that along with the minimizing of fluoro-containing group carbon number, the serviceability of the water-proof and oil-proof composition of preparation declines, and is difficult to reach the level of perfluoro capryl.
Summary of the invention
The technical problem to be solved in the present invention is the defect that overcomes prior art, and the good leather of a kind of waterproof and oilproof performance novel environment friendly water and oil repellent agent is provided.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: a kind of leather novel environment friendly water and oil repellent agent, composed of the following components by weight:
Described fluorochemical monomer is the perfluoro alkene oxygen base monomer that oligomerization of hexafluoropropylene body and hydroxyl monomer reaction obtain.
Described perfluoro alkene oxygen base monomer is CH
2=CHCH
2oC
9f
17, CH
2=CHCOO (CH
2)
2oC
9f
17, CH
2=CHCH
2oC
6f
11, CH
2=CHCH
2oC
6h
4cH
2oC
6f
11, CH
2=CHCH
2oC
6h
4cH
2oC
9f
17, CH
2=C (CH
3) COO (CH
2)
2oC
9f
17, CH
2=CHCOO (CH
2)
3oC
6f
11in one or both mixture.
Described alkyl acrylate is CH
2=CHCOOC
18h
37, CH
2=CHCOOC
12h
25, CH
2=C (CH
3) COOC
18h
37in a kind of.
Described non-fluorochemical monomer is one or both the mixture in methyl acrylate, methyl methacrylate, styrene, hydroxy-ethyl acrylate, Methacrylamide, glycidyl acrylate.
Described initator is preferably a kind of in azodiisobutyronitrile, benzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide.
Described solvent is preferably a kind of in ethyl acetate, methyl iso-butyl ketone (MIBK).
Leather of the present invention novel environment friendly water and oil repellent agent, waterproof and oilproof performance is good.Water and oil repellent agent of the present invention is containing environment being had to perfluoro caprylic acid compounds (PFOA) and the perfluoro octyl sulfonic acid compounds (PFOS) of negative effect, applicable to natural leather and synthetic leather product, the leather surface treatment agent that composition of waterproofing and oil-proof agent of the present invention has been added in employing is coated with processing to leather surface, can make the leather of processing obtain good waterproof oil-proof result.
The compound that described fluorochemical monomer can select following formula (1) to represent:
CH
2=CR—Q—O—R
f（1）
In formula (1), R represents hydrogen atom or methyl; Q represents divalent organic base, as (CH
2)
n, COO (CH
2)
n, (CH
2)
noC
6h
4cH
2deng, n is 1～4; R
fthe perfluor that expression is formed by oligomerization of hexafluoropropylene body, as the perfluor hexenyl (C of dimer formation
6f
11) and the perfluorinated nonene base (C that forms of tripolymer
9f
17).
Described fluorochemical monomer object lesson includes but not limited to following compounds:
CH
2=CRCH
2OC
6F
11
CH
2=CRCH
2OC
9F
17
CH
2=CRCOO(CH
2)
2OC
6F
11
CH
2=CRCOO(CH
2)
3OC
6F
11
CH
2=CRCOO(CH
2)
2OC
9F
17
CH
2=CRCOO(CH
2)
3OC
9F
17
CH
2=CRCH
2OC
6H
4CH
2OC
6F
11
CH
2=CRCH
2OC
6H
4CH
2OC
9F
17
In formula, R represents hydrogen atom or methyl.
Described fluorochemical monomer is preferably the perfluoro alkene oxygen base monomer that oligomerization of hexafluoropropylene body and hydroxyl monomer reaction obtain, and is preferably CH
2=CHCH
2oC
9f
17, CH
2=CHCOO (CH
2)
2oC
9f
17, CH
2=CHCH
2oC
6f
11, CH
2=CHCH
2oC
6h
4cH
2oC
6f
11, CH
2=CHCH
2oC
6h
4cH
2oC
9f
17, CH
2=C (CH
3) COO (CH
2)
2oC
9f
17, CH
2=CHCOO (CH
2)
3oC
6f
11in one or both mixture.
Described alkyl acrylate is (methyl) acrylic acid C preferably
12～24arrcostab, object lesson has (methyl) dodecylacrylate, (methyl) aliphatic acrylate, (methyl) acrylic acid stearyl, (methyl) acrylic acid docosyl ester etc.Alkyl acrylate is CH more preferably
2=CHCOOC
18h
37, CH
2=CHCOOC
12h
25, CH
2=C (CH
3) COOC
18h
37in a kind of.
The object lesson of described non-fluorochemical monomer has the alkene such as second is rare, propylene, isobutene, the halogen alkene such as vinyl chloride, vinylidene chloride, (methyl) acrylic acid C
1～8arrcostab, (methyl) acrylic acid hydroxy alkyl ester, ethyl acetate, styrene, α-methyl styrene, (methyl) acrylamide and derivative monomer thereof, alkyl vinyl ether, (methyl) glycidyl acrylate etc.Preferably styrene, (methyl) methyl acrylate, (methyl) acrylamide, (methyl) hydroxy-ethyl acrylate, (methyl) glycidyl acrylate.Be preferably one or both the mixture in methyl acrylate, methyl methacrylate, styrene, hydroxy-ethyl acrylate, Methacrylamide, glycidyl acrylate.
Described solvent can be selected from ketone, ester class, hydro carbons, chlorinated hydrocarbon etc.Ketones solvent is as acetone, MEK, methyl iso-butyl ketone (MIBK) etc., and esters solvent is as ethyl acetate, butyl acetate etc., and varsol is as hexane, heptane, benzinum etc., and halogenated hydrocarbon solvent is as trichloroethanes, trichorotrifluoroethane etc.Solvent is preferably a kind of in ethyl acetate, methyl iso-butyl ketone (MIBK)
Leather of the present invention is as follows by the preparation method of novel environment friendly water and oil repellent agent: at the temperature of 60 ℃～100 ℃, above-mentioned polymerization single polymerization monomer is carried out to free radical solution copolymerization, thereby make leather of the present invention novel environment friendly water and oil repellent agent.
The initator that polymerization adopts can be selected from oil-soluble azo compound or organic peroxy compounds.Azo is as azodiisobutyronitrile etc., and organic peroxy class is as benzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-t-butyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid tertiary butyl ester etc.Described initator is preferably a kind of in azodiisobutyronitrile, benzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide.
Compared with prior art, the present invention has the following advantages:
1, product waterproof and oilproof performance is good, and the leather water-proof grade after processing is 5 grades, and grease proofing grade is more than 7 grades;
2, safety and environmental protection, containing environment being had to perfluoro caprylic acid compounds (PFOA) and the perfluoro octyl sulfonic acid compounds (PFOS) of negative effect.
The specific embodiment
Below in conjunction with specific embodiment, further illustrate the present invention.But these embodiment are only for explaining the present invention, rather than for limiting the scope of the invention.
Embodiment 1
To the CH that adds 35g in the reaction bulb of 250ml
2=CHCH
2oC
9f
17, 15g CH
2=CHCOOC
18h
37, the methyl acrylate of 10g is, the ethyl acetate of the azodiisobutyronitrile of 0.6g and 90g, under agitation, in 70 ℃ of reactions 15 hours, is cooled to normal temperature, obtains leather novel environment friendly water and oil repellent agent.
Embodiment 2
Remove the CH of 35g
2=CHCH
2oC
9f
17use CH
2=CHCOO (CH
2)
2oC
9f
17outside replacement, all the other are with embodiment 1.
Embodiment 3
Remove the CH of 35g
2=CHCH
2oC
9f
17use 15g CH
2=CHCH
2oC
9f
17with 20g CH
2=CHCH
2oC
6f
11outside replacement, all the other are with embodiment 1.
Embodiment 4
To the CH that adds 51g in the reaction bulb of 250ml
2=CHCOO (CH
2)
2oC
9f
17, 7.8g CH
2=CHCOOC
18h
37, the methyl acrylate of 1.2g is, the ethyl acetate of the benzoyl peroxide of 0.6g and 90g, under agitation, in 100 ℃ of reactions 5 hours, is cooled to normal temperature, leather novel environment friendly water and oil repellent agent.
Embodiment 5
To the CH that adds 45g in the reaction bulb of 250ml
2=CHCOO (CH
2)
2oC
9f
17, 13g CH
2=CHCOOC
12h
25, the styrene of 2g is, the methyl iso-butyl ketone (MIBK) of the lauroyl peroxide of 0.6g and 90g, under agitation, in 80 ℃ of reactions 10 hours, is cooled to normal temperature, obtains leather novel environment friendly water and oil repellent agent.
Embodiment 6
Except reaction temperature is that 60 ℃, reaction time are 20 hours, all the other are with embodiment 5.
Embodiment 7
Remove the CH of 45g
2=CHCOO (CH
2)
2oC
9f
17use CH
2=CHCH
2oC
6h
4cH
2oC
6f
11outside substituting, all the other are with embodiment 5.
Embodiment 8
Remove the CH of 45g
2=CHCOO (CH
2)
2oC
9f
17use CH
2=CHCH
2oC
6h
4cH
2oC
9f
17outside substituting, all the other are with embodiment 5.
Embodiment 9
Except the styrene of 2g is substituted with hydroxy-ethyl acrylate, all the other are with embodiment 5.
Embodiment 10
To the CH that adds 18g in the reaction bulb of 250ml
2=C (CH
3) COO (CH
2)
2oC
9f
17, 39g CH
2=C (CH
3) COOC
18h
37, the styrene of 2g is, the isopropyl benzene hydroperoxide of the Methacrylamide of 1g, 0.6g and the methyl iso-butyl ketone (MIBK) of 90g, under agitation, in 70 ℃ of reactions 15 hours, is cooled to normal temperature, obtains leather novel environment friendly water and oil repellent agent.
Embodiment 11
To the CH that adds 25g in the reaction bulb of 250ml
2=CHCOO (CH
2)
2oC
9f
17, 28g CH
2=CHCOOC
18h
37, the glycidyl acrylate of 7g is, the methyl iso-butyl ketone (MIBK) of the tert-butyl hydroperoxide of 0.6g and 90g, under agitation, in 90 ℃ of reactions 8 hours, is cooled to normal temperature, obtains leather novel environment friendly water and oil repellent agent.
Embodiment 12
To the CH that adds 30g in the reaction bulb of 250ml
2=CHCOO (CH
2)
2oC
9f
17, 21g CH
2=CHCOOC
18h
37, the hydroxy-ethyl acrylate of 7g is, the methyl iso-butyl ketone (MIBK) of the azodiisobutyronitrile of 0.6g and 90g, under agitation, in 80 ℃ of reactions 10 hours, is cooled to normal temperature, obtains leather novel environment friendly water and oil repellent agent.
Embodiment 13
To the CH that adds 4g in the reaction bulb of 250ml
2=CHCOO (CH
2)
2oC
9f
17, 3g CH
2=CHCOOC
18h
37, the styrene of 1g is, the methyl iso-butyl ketone (MIBK) of the azodiisobutyronitrile of 0.08g and 152g, under agitation, in 80 ℃ of reactions 10 hours, is cooled to normal temperature, leather novel environment friendly water and oil repellent agent.
Embodiment 14
To the CH that adds 20g in the reaction bulb of 250ml
2=CHCOO (CH
2)
2oC
9f
17, 15g CH
2=CHCOOC
18h
37, the styrene of 5g is, the methyl iso-butyl ketone (MIBK) of the azodiisobutyronitrile of 0.4g and 120g, under agitation, in 80 ℃ of reactions 10 hours, is cooled to normal temperature, obtains leather novel environment friendly water and oil repellent agent.
Embodiment 15
To the CH that adds 40g in the reaction bulb of 250ml
2=CHCOO (CH
2)
2oC
9f
17, 15g CH
2=CHCOOC
18h
37, the styrene of 5g is, the methyl iso-butyl ketone (MIBK) of the azodiisobutyronitrile of 0.6g and 90g, under agitation, in 80 ℃ of reactions 10 hours, is cooled to normal temperature, obtains leather novel environment friendly water and oil repellent agent.
Embodiment 16
Except the styrene of 5g is substituted with methyl methacrylate, all the other are with embodiment 15.
Embodiment 17
Remove the CH of 40g
2=CHCOO (CH
2)
2oC
9f
17use CH
2=CHCOO (CH
2)
3oC
6f
11outside substituting, all the other are with embodiment 15.
Embodiment 18
Remove the CH of 40g
2=CHCOO (CH
2)
2oC
9f
17use CH
2=CHCH
2oC
6h
4cH
2oC
9f
17outside substituting, all the other are with embodiment 15.
Embodiment 19
To the CH that adds 54g in the reaction bulb of 250ml
2=CHCOO (CH
2)
2oC
9f
17, 40g CH
2=CHCOOC
18h
37, the styrene of 10g is, the methyl iso-butyl ketone (MIBK) of the azodiisobutyronitrile of 1g and 56g, under agitation, in 80 ℃ of reactions 10 hours, is cooled to normal temperature, obtains leather novel environment friendly water and oil repellent agent.
Embodiment 20
To the CH that adds 8g in the reaction bulb of 250ml
2=CHCOO (CH
2)
2oC
9f
17, 6g CH
2=CHCOOC
18h
37, the styrene of 2g is, the methyl iso-butyl ketone (MIBK) of the azodiisobutyronitrile of 0.16g and 144g, under agitation, in 80 ℃ of reactions 10 hours, is cooled to normal temperature, obtains leather novel environment friendly water and oil repellent agent.
Embodiment 21
To the CH that adds 35g in the reaction bulb of 250ml
2=CHCOO (CH
2)
2oC
9f
17, 20g CH
2=CHCOOC
18h
37, the styrene of 5g is, the methyl iso-butyl ketone (MIBK) of the azodiisobutyronitrile of 0.6g and 90g, under agitation, in 80 ℃ of reactions 10 hours, is cooled to normal temperature, obtains leather novel environment friendly water and oil repellent agent.
Embodiment 22
Except the styrene of 5g is substituted with the methyl acrylate of 3g and the hydroxy-ethyl acrylate of 2g, all the other are with embodiment 21.
Embodiment 23
To the CH that adds 40g in the reaction bulb of 250ml
2=CHCOO (CH
2)
2oC
9f
17, 30g CH
2=CHCOOC
18h
37, the styrene of 10g is, the methyl iso-butyl ketone (MIBK) of the azodiisobutyronitrile of 0.8g and 80g, under agitation, in 80 ℃ of reactions 10 hours, is cooled to normal temperature, leather novel environment friendly water and oil repellent agent.
Comparative example 1
To the CH that adds 45g in the reaction bulb of 250ml
2=C (CH
3) COOCH
2cH
2c
4f
9, 13g CH
2=C (CH
3) COOC
18h
37, the n-BMA of 2g is, the methyl iso-butyl ketone (MIBK) of the azodiisobutyronitrile of 0.6g and 90g, under agitation, in 80 ℃ of reactions 10 hours, is cooled to normal temperature, obtains water and oil repellent agent.
Comparative example 2
Remove the CH of 45g
2=C (CH
3) COOCH
2cH
2c
4f
9use CH
2=C (CH
3) COOCH
2cH
2c
6f
13outside substituting, all the other are with comparative example 1.
The leather of the embodiment of the present invention 1～23 preparation is joined to leather surface treatment agent with the water and oil repellent agent of preparation in novel environment friendly water and oil repellent agent and comparative example 1～2 and (claim again leather surface layer PU slurry, Fujian province inspires confidence in Chemical Co., Ltd. to be provided) in, be configured to treatment fluid.Then with the treatment fluid being configured to, PU artificial leather (Fujian province inspires confidence in Chemical Co., Ltd. to be provided) is carried out to surface treatment, handling process is as follows:
(1) configuration for the treatment of fluid
Water and oil repellent agent is added in leather surface treatment agent, stir, be configured to treatment fluid, stand-by.The addition of water and oil repellent agent active ingredient accounts for 2% of leather surface treatment agent quality.The water and oil repellent agent active ingredient here refers to other composition that desolventizes outer water and oil repellent agent.
(2) coating leather and dry
By the treatment fluid mixing by 1g/100cm
2coating weight be coated with, then coating leather is put into the baking oven of 90～120 ℃ and processes 3～15 minutes.
To processing the waterproof and oilproof performance of rear leather, evaluate, acquired results refers to table 3, wherein:
Water proofing property evaluation criterion is pressed GB/T4745-1997 < < textile fabric surface moisture resistance and is measured dip experiment > > execution;
Grease proofness evaluation criterion is pressed the anti-hydrocarbon test of GB/T19977-2005 < < textiles oil repellent > > and is carried out.Table 1 water proofing property evaluation criterion: GB/T4745-1997 textile fabric surface moisture resistance is measured dip experiment.
| Classification of waterproof | State |
| 5 | Surface is without moistening |
| 4 | Surface is moistening on a small quantity |
| 3 | Surface fractional wettability |
| 2 | Surface wettability |
| 1 | Surface is all moistening |
Table 2 grease proofness evaluation criterion: the anti-hydrocarbon test of GB/T19977-2005 textiles oil repellent.
| Numbering | Experimental liquid forms | Surface tension (N/m, 25 ℃) |
| 8 | Normal heptane | 0.0198 |
| 7 | Normal octane | 0.0214 |
| 6 | N-decane | 0.0235 |
| 5 | N-dodecane | 0.0247 |
| 4 | N-tetradecane | 0.0264 |
| 3 | Hexadecane | 0.0273 |
| 2 | Hexadecane 35/ white mineral oil 65 mixed liquors | 0.0296 |
| 1 | White mineral oil | 0.0315 |
Table 3 is evaluated by the waterproof and oilproof performance that the water and oil repellent agent of embodiment 1～23 and comparative example 1～2 is processed rear leather
| Embodiment | Classification of waterproof | Grease proofing grade |
| 1 | 5 | 8 |
| 2 | 5 | 8 |
| 3 | 5 | 8 |
| 4 | 5 | 8 |
| 5 | 5 | 7 |
| 6 | 5 | 8 |
| 7 | 5 | 8 |
| 8 | 5 | 8 |
| 9 | 5 | 8 |
| 10 | 5 | 7 |
| 11 | 5 | 8 |
| 12 | 5 | 8 |
| 13 | 5 | 8 |
| 14 | 5 | 8 |
| 15 | 5 | 8 |
| 16 | 5 | 8 |
| 17 | 5 | 7 |
| 18 | 5 | 8 |
| 19 | 5 | 8 |
| 20 | 5 | 8 |
| 21 | 5 | 8 |
| 22 | 5 | 7 |
| 23 | 5 | 8 |
| Blank | 1 | 0 |
| Comparative example 1 | 3 | 4 |
| Comparative example 2 | 3 | 4 |
Note: blank is the leather of unprocessed mistake.
Claims (7)
1. a leather novel environment friendly water and oil repellent agent, composed of the following components by weight:
。
2. leather according to claim 1 novel environment friendly water and oil repellent agent, is characterized in that described fluorochemical monomer is the perfluoro alkene oxygen base monomer that oligomerization of hexafluoropropylene body and hydroxyl monomer reaction obtain.
3. leather according to claim 2 novel environment friendly water and oil repellent agent, is characterized in that described perfluoro alkene oxygen base monomer is CH
2=CHCH
2oC
9f
17, CH
2=CHCOO (CH
2)
2oC
9f
17, CH
2=CHCH
2oC
6f
11, CH
2=CHCH
2oC
6h
4cH
2oC
6f
11, CH
2=CHCH
2oC
6h
4cH
2oC
9f
17, CH
2=C (CH
3) COO (CH
2)
2oC
9f
17, CH
2=CHCOO (CH
2)
3oC
6f
11in one or both mixture.
4. leather according to claim 1 novel environment friendly water and oil repellent agent, is characterized in that described alkyl acrylate is CH
2=CHCOOC
18h
37, CH
2=CHCOOC
12h
25, CH
2=C (CH
3) COOC
18h
37in a kind of.
5. leather according to claim 1 novel environment friendly water and oil repellent agent, is characterized in that described non-fluorochemical monomer is one or both the mixture in methyl acrylate, methyl methacrylate, styrene, hydroxy-ethyl acrylate, Methacrylamide, glycidyl acrylate.
6. leather according to claim 1 novel environment friendly water and oil repellent agent, is characterized in that described initator is a kind of in azodiisobutyronitrile, benzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide.
7. leather according to claim 1 novel environment friendly water and oil repellent agent, is characterized in that described solvent is a kind of in ethyl acetate, methyl iso-butyl ketone (MIBK).
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|---|---|---|---|
| CN201310535905.4A CN103757915A (en) | 2013-11-01 | 2013-11-01 | Novel environment-friendly oil and water repellent agent for leather |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310535905.4A CN103757915A (en) | 2013-11-01 | 2013-11-01 | Novel environment-friendly oil and water repellent agent for leather |
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Cited By (6)
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| CN104262151A (en) * | 2014-09-19 | 2015-01-07 | 广东希贵光固化材料有限公司 | Fluorine-containing photocuring monomer and preparation method thereof |
| CN105969031A (en) * | 2016-05-26 | 2016-09-28 | 清远市美乐仕油墨有限公司 | Environment-friendly flame-retardant waterproof agent for leather and preparation method of environment-friendly flame-retardant waterproof agent |
| CN106085222A (en) * | 2016-07-12 | 2016-11-09 | 广州双桃精细化工有限公司 | A kind of leather environmental protection flame retardant waterproofing agent and preparation method thereof |
| CN108286207A (en) * | 2017-12-18 | 2018-07-17 | 巨化集团技术中心 | A kind of paper products water and oil repellent agent and preparation method thereof |
| CN109180858A (en) * | 2018-10-25 | 2019-01-11 | 中国科学技术大学 | Modifying agent, double thin BC class ultra-fine dry powder extinguishing agents and preparation method thereof |
| CN113322693A (en) * | 2021-05-26 | 2021-08-31 | 广东菲安妮皮具股份有限公司 | Waterproof and oil-proof leather and preparation method thereof |
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| CN104262151A (en) * | 2014-09-19 | 2015-01-07 | 广东希贵光固化材料有限公司 | Fluorine-containing photocuring monomer and preparation method thereof |
| CN105969031A (en) * | 2016-05-26 | 2016-09-28 | 清远市美乐仕油墨有限公司 | Environment-friendly flame-retardant waterproof agent for leather and preparation method of environment-friendly flame-retardant waterproof agent |
| CN105969031B (en) * | 2016-05-26 | 2018-05-15 | 清远市美佳乐环保新材股份有限公司 | A kind of leather environmental protection flame retardant waterproofing agent and preparation method thereof |
| CN106085222A (en) * | 2016-07-12 | 2016-11-09 | 广州双桃精细化工有限公司 | A kind of leather environmental protection flame retardant waterproofing agent and preparation method thereof |
| CN108286207A (en) * | 2017-12-18 | 2018-07-17 | 巨化集团技术中心 | A kind of paper products water and oil repellent agent and preparation method thereof |
| CN109180858A (en) * | 2018-10-25 | 2019-01-11 | 中国科学技术大学 | Modifying agent, double thin BC class ultra-fine dry powder extinguishing agents and preparation method thereof |
| CN113322693A (en) * | 2021-05-26 | 2021-08-31 | 广东菲安妮皮具股份有限公司 | Waterproof and oil-proof leather and preparation method thereof |
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