CN1952035A - Phosphate water, oil-repellent containing fluoroolefin and its preparation method and uses - Google Patents
Phosphate water, oil-repellent containing fluoroolefin and its preparation method and uses Download PDFInfo
- Publication number
- CN1952035A CN1952035A CN200610069165.XA CN200610069165A CN1952035A CN 1952035 A CN1952035 A CN 1952035A CN 200610069165 A CN200610069165 A CN 200610069165A CN 1952035 A CN1952035 A CN 1952035A
- Authority
- CN
- China
- Prior art keywords
- water
- phosphoric acid
- repellent
- base
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000005871 repellent Substances 0.000 title claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 47
- 229910019142 PO4 Inorganic materials 0.000 title description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title 1
- 239000010452 phosphate Substances 0.000 title 1
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000011737 fluorine Substances 0.000 claims abstract description 25
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- 125000000962 organic group Chemical group 0.000 claims abstract description 10
- -1 perfluoro side chain alkenes Chemical class 0.000 claims abstract description 8
- 230000001788 irregular Effects 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 239000010985 leather Substances 0.000 claims abstract description 5
- 239000002585 base Substances 0.000 claims description 46
- 150000003016 phosphoric acids Chemical class 0.000 claims description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000004945 emulsification Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000002940 repellent Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 239000008267 milk Substances 0.000 claims 1
- 210000004080 milk Anatomy 0.000 claims 1
- 235000013336 milk Nutrition 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 28
- 239000000123 paper Substances 0.000 abstract description 13
- 239000000835 fiber Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000010953 base metal Substances 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 239000002023 wood Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000839 emulsion Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005065 mining Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical class CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- QLPAUYNUTUADDO-UHFFFAOYSA-N 2-aminoethanol;bis(2-ethylhexyl) hydrogen phosphate Chemical compound NCCO.CCCCC(CC)COP(O)(=O)OCC(CC)CCCC QLPAUYNUTUADDO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009954 braiding Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000002500 effect on skin Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 235000011182 sodium carbonates Nutrition 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CALBFTKHOHKQIA-UHFFFAOYSA-N N(CCO)CCO.[P] Chemical compound N(CCO)CCO.[P] CALBFTKHOHKQIA-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- RFCKRIWTGOTBLT-UHFFFAOYSA-L disodium dihydrogen phosphate hydrogen carbonate Chemical compound [Na+].[Na+].OC(O)=O.OP([O-])([O-])=O RFCKRIWTGOTBLT-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical class [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Paper (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
There is provided a phosphas agent with alkenes base that contains fluorine. The agent can resist aqua and oils, the preparation and the application of the agent is also disclosed in the invention. The general formula of the phosphas is [RfQ]m[OH]n[Y+O-]kP=O. While in the formula, Rf stands for perfluoro side chain alkenes base; Q stands for divalent organic group; Y+ stands for (N+HR1R2R3) or base metal iron, of which R1, R2, R3 stand for H atom or -CH2CH2OH (m= integer from 1-3, n=integer from 0-2, k=integer form 0-2, m+n+k=3). The invention can assign the base material excellent quality of resisting aqua and oils. It has no special restriction to the base materials but it's preferable to use base materials which have irregular fiber tissues such as paper, leather and wood.
Description
Technical field
The invention belongs to the tensio-active agent field, relate to the processing that is used for base material, the fluorochemical surfactant of giving the good water and oil repellant performance of base material.Relate in particular to the good water and oil repellants of the irregular base material of fibrage such as a kind of low temperature resistant paper given, timber, leather and do not cause the fluorine-containing water-repellent oil-repellent agent of phosphoric acid salt of the Fluorine containing olefine base of other performance variation.
Background technology
At present, people have known that coating substrate surface with the water repellency material with low surface tension carries out the water and oil repellant processing.For example, with not hydrophilic wax class; Processing base materials such as acrylic acid or the like or vinyl macromolecular compound or type siloxane make it possess the difficult performance that is bedewed or soak into by water, though above-mentioned hydrocarbon compound or siloxanes can be given not wetting ability of base material, but can not give its oil repellent energy.
Contain Polyfluoroalkyl and (following Polyfluoroalkyl is called R
fBase) material can be given base material and have the water of refusing and oil repellent energy simultaneously, and possessing of the performance of this water and oil repellant mainly is because R
fBase is arranged at the surface crystallization of base material, and the sealing coat that forms low surface tension causes.Therefore, have water and oil repellant, can adopt foregoing two kinds of methods, promptly (following Polyfluoroalkyl is called R with containing Polyfluoroalkyl for making base material
fBase) high molecular polymer or low molecular compound carry out surface dressing to base material.
For example, Chinese patent application CN1116857 provides a kind of manufacture method of water-repellent oil-repellent agent, utilization contains in the group that the hydrogenation hydrofluoric ether of number of fluorine atoms more than 4 by the hydrogenation chloro hydrofluoric ether of boiling point 0-150 ℃ carbonatoms 2-3 and carbonatoms 4-6 of 5% weight form selects at least a compound as polymer solvent, with at least a monomer that contains poly-fluoroalkyl with have the possible monomer component of polymerization in this polymer solvent, to carry out solution polymerization.Though this method available is water-repellent oil-repellent agent preferably, its solutions employed polymerization process cost height, and solvent can cause environmental pollution and human body harm by volatilization in the product application process.Chinese patent application CN86101691 has introduced a kind of water-repellent oil-repellent agent, it is to comprise that the acrylate that contains at least one perfluor alkane or perfluorinated alkylidene or methacrylate monomer compound and a kind of second-order transition temperature are not less than the co-polymer of 115 ℃ methacrylic acid monomer, this water and oil repellent agent has good dry cleaning resistance and anti-slipping property, but it mainly is applicable to the water and oil repellent finish of natural or rayon.
In sum, for fibrage very clocklike base material such as fabric etc., adopt the high molecular polymer water-refusing oil-refusing finishing agent that contains fluoroalkyl proper.The water and oil repellant principle of it and micromolecular fluorine-containing alkylate is different, by making base material have the water and oil repellant performance in the film forming mode of the fiber surface of regular braiding.Micromolecular fluorine-containing alkylate then relatively is suitable for the irregular base material of fibrage, as paper, leather or timber etc., it can by with fiber on the effect of polar group by the chemical combination key be attached on the fiber, because the solid surface ability has the trend that reduces automatically, perfluoroalkyl has extremely low surface energy, so it has the trend that stretches than other group in air, promptly so-called " skin effect problem ".By this " skin effect problem ", micromolecular fluorine-containing alkylate can form a sealing coat on the surface of irregular braiding on microtexture, play the effect of water and oil repellant.Provide a kind of small molecules water and oil repellant compound with the immediate Chinese patent application CN1302319A of this patent, even being a kind of freeze-thawing repeatedly, it can not cause that big viscosity changes, the fluorine-containing alkyl phosphate salt compounds of the aqueous dispersion type of storage stability excellence yet, but the fluoroalkyl that contains of this compound is the alkyl with saturated structures, and its production cost is than higher.
Summary of the invention
The purpose of this invention is to provide a kind of production cost fluorine-containing phosphoric acid salt water-repellent oil-repellent agent and application thereof low, that base material is not particularly limited.
The invention provides a kind of phosphates water-repellent oil-repellent agent of Fluorine containing olefine base, wherein the phosphoric acid salt general formula of Fluorine containing olefine base is: [R
fQ]
m[OH]
n[Y
+O
-]
kP=O;
In the formula, R
f=perfluor branched-chain alkene base, the Q=divalent organic group;
Y
+=(N
+HR
1R
2R
3) or alkali metal cation, wherein R
1, R
2, R
3The expression H atom or-CH
2CH
2OH;
The integer of m=1～3, the integer of n=0～2, the integer of k=0～2, and m+n+k=3.
The microcosmic salt class water-repellent oil-repellent agent of Fluorine containing olefine base provided by the invention is that concentration is the aqueous emulsion type of 10-50%.
R in the phosphoric acid salt of Perfluoralkylene-containing
fBe meant the undersaturated side chain Perfluoralkylene of 3-12 carbon atom, if less than 2, then there is the oil-proofness downward trend in carbonatoms, if surpass 12, then compound becomes solid at normal temperatures, is difficult to emulsification.R
fThe perfluor branched-chain alkene base of preferred 4-12 carbon atom, the more preferably perfluor branched-chain alkene base of 6-10 carbon atom, its production cost is low and be good water and oil repellant group.
R
fObject lesson C is arranged
3F
5-, C
4F
7-, C
6F
11-, C
8F
15-, C
9F
17-, C
10F
19-, C
12F
23-, C most preferably wherein
6F
11-, C
8F
15-, C
9F
17-, C
10F
19-.
M in the phosphoric acid salt of Perfluoralkylene-containing, n, k are respectively integers, m=1～3, n=0～2, k=0～2, and m+n+k=3, preferred m=1, n=1.
Q in the phosphoric acid salt of Perfluoralkylene-containing is a divalent organic group, preferably has the binary alcohol radical or the binary phenolic group of 2-6 carbon atom, and the Q optimum is-OCH
2CH
2O-or-OC
6H
4O-.
Y in the phosphoric acid salt of Perfluoralkylene-containing
+Be (N
+HR
1R
2R
3) or alkali metal cation.R wherein
1, R
2, R
3Independently represent respectively the H atom or-CH
2CH
2The OH alkali metal cation is Na
+, K
+Deng.Y
+Preferred R
1Be hydrogen, R
2And R
3For-CH
2CH
2(the N of OH
+HR
1R
2R
3).
The phosphatic object lesson of Perfluoralkylene-containing has following compound, and Perfluoralkylene wherein can be any in the isomery group.
[C
3F
5OCH
2CH
2O]
2[N
+H
2(CH
2CH
2OH)O
-]P＝O
[C
4F
7OCH
2CH
2O][N
+H
2(CH
2CH
2OH)O
-]
2P＝O
[C
6F
11OC
6H
5O][OH][N
+H
2(CH
2CH
2OH)O
-]P＝O
[C
8F
15OCH
2CH
2O]
2[N
+H
2(CH
2CH
2OH)O
-]P＝O
[C
9F
17OCH
2CH
2O][OH][N
+H
2(CH
2CH
2OH)O
-]P＝O
[C
9F
17OC
6H
5O][ONa
+][N
+H
2(CH
2CH
2OH)O
-]P＝O
[C
10F
19OCH
2CH
2O][N
+H
2(CH
2CH
2OH)O
-]
2P＝O
[C
12F
23OC
6H
5O][OH][N
+H
2(CH
2CH
2OH)O
-]P＝O
The present invention also provides a kind of preparation method of phosphoric acid salt water-repellent oil-repellent agent of described Fluorine containing olefine base, comprises the following steps:
1) reaction of perfluoroolefine and divalent organic group: perfluoroolefine, acid binding agent and divalent organic group are packed in the reactor, be heated to 40-45 ℃, reacted 4-6 hour, product is poured in the frozen water washed then, obtain the fluoroolefin base intermediate of hydroxyl.
2) phosphating reaction: the fluoroolefin intermediate and two polyphosphoric acids of the hydroxyl that step 1) is obtained carried out under 70-90 ℃ of condition esterification 5-6 hour, were hydrolyzed under this temperature 2 hours then, obtained the phosphoric acid ester of Perfluoralkylene-containing.
3) neutralization reaction: with step 2) phosphoric acid ester of the Perfluoralkylene-containing that obtains and mineral alkali or organic bases carried out neutralization reaction 2-4 hour, obtained the phosphoric acid salt of Perfluoralkylene-containing.
4) preparation of water and oil repellant water miscible liquid: the phosphoric acid salt and the water of Perfluoralkylene-containing are carried out the phosphatic water miscible liquid that emulsification obtains Perfluoralkylene.
Contain the undersaturated side chain perfluoroolefine that perfluoroolefine is meant 3-12 carbon atom, the perfluor branched-chain alkene of preferred 4-12 carbon atom, more preferably the perfluor branched-chain alkene of 6-10 carbon atom described in the step 1).Object lesson has C
3F
6, C
4F
8, C
6F
12, C
8F
16, C
9F
18, C
10F
20, C
12F
24, C most preferably wherein
6F
12, C
8F
16, C
9F
18, C
10F
20Deng.
Divalent organic group described in the step 1) preferably has the dibasic alcohol or the dihydric phenol of 2-6 carbon atom, and optimum is HOCH
2CH
2OH or HOC
6H
4OH.
Acid binding agent described in the step 1) is selected from a kind of in triethylamine, diethylamine, the ethamine, preferred triethylamine.
Mineral alkali described in the step 3) or organic bases are selected from a kind of in thanomin, diethanolamine, trolamine, yellow soda ash, the salt of wormwood, preferred trolamine.
Mode makes each component fully disperse or mix.The most handy high-pressure emulsification machine, fluid shearing machine, Micro Fluid device etc. carry out high-pressure emulsification.Pressure during high-pressure emulsification is preferably 10-50MP, and temperature is preferably the 20-80 degree.During high-pressure emulsification, can carry out pre-dispersed or pre-emulsification as required, to improve the high-pressure emulsification effect.
The phosphates water-repellent oil-repellent agent of Fluorine containing olefine base of the present invention can stably be given the water and oil repellant performance of base material excellence, base material is not particularly limited, but the irregular base materials of fibrage such as preferred paper, leather or timber.
Embodiment
Following examples are that preparation and the application to the phosphates water-repellent oil-repellent agent of Fluorine containing olefine base of the present invention is described further.
Embodiment 1
Add the ethylene glycol of 75.24 grams and the triethylamine of 122.28 grams in 4 mouthfuls of glass flask of 500 milliliters that agitator, constant pressure funnel, condensing reflux pipe, thermometer are housed, temperature rises to 40 degree, begins to drip the perfluor hexene C of 300.5 grams
6F
12, dropwise in 1 hour, react and after 4 hours product is washed with water to neutrality, obtain the C of about 321.58 grams
6F
11OCH
2CH
2OH.
In 4 mouthfuls of glass flask of 500 milliliters that agitator, constant pressure funnel, condensing reflux pipe, thermometer are housed, add 72.9 two polyphosphoric acids that restrain, drip the reaction product of previous step then, reaction is 6 hours under 80 degree conditions, obtain light yellow viscous liquid, then add 10mL water and under this temperature, be hydrolyzed 2 hours.Reduce to room temperature then, the diethanolamine aqueous solution 20mL of amount of substances such as adding stirred 2 hours, obtained containing perfluor hexene oxyethyl group phosphoric acid salt dispersion liquid.
Above-mentioned dispersion liquid is added suitable quantity of water, its concentration is reached about 30%, under 20MP pressure, carry out emulsification with high pressure homogenizer then, obtain containing perfluor hexene oxyethyl group di(2-ethylhexyl)phosphate ethanolamine salt emulsion.
The method handling of paper of adding in adopting, oven dry under 120 degree then, by the Kit of Minnesota Mining and Manufacturing Company water and oil repellant test experience method, the Kit number is big more, illustrates that the water and oil repellant performance is strong more.Detect its performance, application result sees Table 1.
Embodiment 2
Add the ethylene glycol of 75.24 grams and the triethylamine of 122.28 grams in 4 mouthfuls of glass flask of 500 milliliters that agitator, constant pressure funnel, condensing reflux pipe, thermometer are housed, temperature rises to 40 degree, begins to drip the perfluorinated nonene C of 450.0 grams
9F
18, dropwise in 1 hour, react and after 4 hours product is washed with water to neutrality, obtain the C of about 470.1 grams
9F
18OCH
2CH
2OH.
In 4 mouthfuls of glass flask of 500 milliliters that agitator, constant pressure funnel, condensing reflux pipe, thermometer are housed, add 72.9 two polyphosphoric acids that restrain, drip the reaction product of previous step then, reaction is 6 hours under 80 degree conditions, obtain light yellow viscous liquid, then add 10mL water and under this temperature, be hydrolyzed 2 hours.Reduce to room temperature then, the aqueous sodium carbonate 20mL of amount of substances such as adding stirred 2 hours, obtained containing perfluorinated nonene oxyethyl group sodium phosphate salt dispersion liquid.
Above-mentioned dispersion liquid is added suitable quantity of water, its concentration is reached about 25%, under 30MP pressure, carry out emulsification with high pressure homogenizer then, obtain containing perfluorinated nonene oxyethyl group phosphoric acid sodium carbonate salt emulsion.
The method handling of paper of adding in adopting, oven dry under 120 degree then, application result sees Table 1.
Embodiment 3
Substitute ethylene glycol with Resorcinol, other is identical with example 1, obtains perfluorinated nonene phenoxy group di(2-ethylhexyl)phosphate ethanolamine salt emulsion, the method handling of paper of adding in adopting, and oven dry under 120 degree then, application result sees Table 1.
Embodiment 4
Use C
10F
20Replaced C
9F
18Other is identical with example 1, obtains containing perfluor certain herbaceous plants with big flowers alkene oxyethyl group sodium phosphate emulsion, the method handling of paper of adding in adopting, and oven dry under 120 degree then, by Minnesota Mining and Manufacturing Company's water and oil repellant test experience method, application result sees Table 1.
Embodiment 5
Substitute ethylene glycol with Resorcinol, other is identical with example 4, obtains containing perfluor alkene phenoxy group sodium phosphate emulsion, the method handling of paper of adding in adopting, and oven dry under 120 degree then, by Minnesota Mining and Manufacturing Company's water and oil repellant test experience method, application result sees Table 1.
Embodiment 6
Other is identical with example 1, but in and the time two times of amount of substances such as addings grade the diethanolamine aqueous solution obtain containing perfluor hexene oxyethyl group di(2-ethylhexyl)phosphate ethanol disalt emulsion, the method handling of paper of adding in adopting, oven dry under 120 degree then, by Minnesota Mining and Manufacturing Company's water and oil repellant test experience method, application result sees Table 1.
Embodiment 7
Other is identical with example 1, but in and the time add two times of aqueous sodium carbonates that wait amount of substances, obtain containing perfluorinated nonene oxyethyl group Di-Sodium Phosphate salinity emulsion, the method handling of paper of adding in adopting, oven dry under 120 degree then, by Minnesota Mining and Manufacturing Company's water and oil repellant test experience method, application result sees Table 1.
Embodiment 8
Use C
4F
8Replaced C
9F
18Other is identical with example 1, obtains containing perfluorobuttene oxyethyl group phosphorus diethanolamine salt emulsion, the method handling of paper of adding in adopting, and oven dry under 120 degree then, by Minnesota Mining and Manufacturing Company's water and oil repellant test experience method, application result sees Table 1.
Embodiment 9
Use C
L2F
24Replaced C
9F
18In and the time add two times of aqueous sodium carbonates that wait amount of substances, other is identical with example 1, obtain containing perfluor laurylene oxyethyl group disodic alkaliine emulsion, the method handling of paper of adding in adopting, oven dry under 120 degree then, by Minnesota Mining and Manufacturing Company's water and oil repellant test experience method, application result sees Table 1.
Table 1
| The test sequence number | Water and oil repellant | |||
| Water repellency | Oil repellent | |||
| Before the arrangement | After the arrangement | Before the arrangement | After the arrangement | |
| Embodiment 1 | 0 | 12 | 0 | 14 |
| Embodiment 2 | 0 | 13 | 0 | 14 |
| Embodiment 3 | 0 | 13 | 0 | 14 |
| Embodiment 4 | 0 | 13 | 0 | 14 |
| Embodiment 5 | 0 | 12 | 0 | 14 |
| Embodiment 6 | 0 | 12 | 0 | 14 |
| Embodiment 7 | 0 | 11 | 0 | 13 |
| Embodiment 8 | 0 | 10 | 0 | 12 |
| Embodiment 9 | 0 | 13 | 0 | 14 |
Claims (9)
1, a kind of phosphoric acid salt water-repellent oil-repellent agent of Perfluoralkylene-containing is characterized in that, contains the phosphoric acid salt of Perfluoralkylene;
The phosphatic general formula of described Perfluoralkylene is: [R
fQ]
m[OH]
n[Y
+O-]
kP=O;
In the formula, R
f=perfluor branched-chain alkene base, the Q=divalent organic group,
Y
+=(N
+HR
1R
2R
3) or alkali metal cation, wherein R
1, R
2, R
3The expression H atom or-CH
2CH
2OH,
The integer of m=1～3, the integer of n=0～2, the integer of k=0～2, and m+n+k=3.
2, the phosphoric acid salt water-repellent oil-repellent agent of Fluorine containing olefine base as claimed in claim 1 is characterized in that R
fPerfluor branched-chain alkene base for 4-12 carbon atom.
3, the phosphoric acid salt water-repellent oil-repellent agent of Fluorine containing olefine base as claimed in claim 1 or 2 is characterized in that, Q is-OCH
2CH
2O-or-OC
6H
4O-.
4, the phosphoric acid salt water-repellent oil-repellent agent of Fluorine containing olefine base as claimed in claim 1 or 2 is characterized in that Y
+Expression (N
+HR
1R
2R
3), R wherein
1, R
2, R
3For the H atom or-CH
2CH
2OH.
5, the phosphoric acid salt water-repellent oil-repellent agent of Fluorine containing olefine base as claimed in claim 1 or 2 is characterized in that, m=1, n=1.
6. the phosphoric acid salt water-repellent oil-repellent agent of Fluorine containing olefine base as claimed in claim 1 or 2 is characterized in that, adopts high pressure homogenizer that the phosphoric acid salt and the water and milk of Fluorine containing olefine base are changed into the water miscible liquid of 10-50% concentration as water-refusing oil-refusing finishing agent.
7. the preparation method of the phosphoric acid salt water-repellent oil-repellent agent of Fluorine containing olefine base as claimed in claim 1 comprises the following steps:
1) reaction of perfluoroolefine and divalent organic group: perfluoroolefine, acid binding agent and divalent organic group are packed in the reactor, be heated to 40-45 ℃, reacted 4-6 hour, product is poured in the frozen water washed then, obtain the fluoroolefin base intermediate of hydroxyl;
2) phosphating reaction: the fluoroolefin intermediate and two polyphosphoric acids of the hydroxyl that step 1) is obtained carried out under 70-90 ℃ of condition esterification 5-6 hour, were hydrolyzed under this temperature 2 hours then, obtained the phosphoric acid ester of Perfluoralkylene-containing;
3) neutralization reaction: with step 2) phosphoric acid ester of the Perfluoralkylene-containing that obtains and mineral alkali or organic bases carried out neutralization reaction 2-4 hour, obtained the phosphoric acid salt of Perfluoralkylene-containing;
4) preparation of water and oil repellant water miscible liquid: the phosphoric acid salt and the water of Perfluoralkylene-containing are carried out the phosphatic water miscible liquid that emulsification obtains Perfluoralkylene.
8. the preparation method of the phosphoric acid salt water-repellent oil-repellent agent of Fluorine containing olefine base as claimed in claim 7 is characterized in that, the described acid binding agent described in the step 1) is selected from a kind of in triethylamine, diethylamine, the ethamine; Divalent organic group described in the step 1) is dibasic alcohol or the dihydric phenol that 2-6 carbon atom arranged; Mineral alkali described in the step 3) or organic bases are selected from a kind of in thanomin, diethanolamine, trolamine, yellow soda ash, the salt of wormwood.
9, the application of the phosphoric acid salt water-repellent oil-repellent agent of Fluorine containing olefine base as claimed in claim 1 or 2 is characterized in that, the phosphatic water miscible liquid of Fluorine containing olefine base can be used for the water and oil repellent finish of the irregular base material of fibrage; The irregular base material of described fibrage is selected from one or more of paper, timber, leather.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610069165.XA CN100560678C (en) | 2006-10-17 | 2006-10-17 | A kind of fluorine-containing olefin-based phosphate water and oil repellent agent and its preparation and application |
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|---|---|---|---|
| CN200610069165.XA CN100560678C (en) | 2006-10-17 | 2006-10-17 | A kind of fluorine-containing olefin-based phosphate water and oil repellent agent and its preparation and application |
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| Publication Number | Publication Date |
|---|---|
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| CN100560678C CN100560678C (en) | 2009-11-18 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102077090A (en) * | 2008-06-30 | 2011-05-25 | 旭硝子株式会社 | Process for analyzing low molecular weight organic compound having at most 20 carbon atoms in cloth made of chemical fibers treated with water and oil repellent agent |
| CN103695578A (en) * | 2013-12-30 | 2014-04-02 | 青昊环保科技（上海）有限公司 | Leather water-proof curing agent and preparing method thereof |
-
2006
- 2006-10-17 CN CN200610069165.XA patent/CN100560678C/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102077090A (en) * | 2008-06-30 | 2011-05-25 | 旭硝子株式会社 | Process for analyzing low molecular weight organic compound having at most 20 carbon atoms in cloth made of chemical fibers treated with water and oil repellent agent |
| CN103695578A (en) * | 2013-12-30 | 2014-04-02 | 青昊环保科技（上海）有限公司 | Leather water-proof curing agent and preparing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100560678C (en) | 2009-11-18 |
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