CN103694414A - Preparation method of fluorine-silicon composite waterproof leather fatliquor - Google Patents
Preparation method of fluorine-silicon composite waterproof leather fatliquor Download PDFInfo
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- CN103694414A CN103694414A CN201310690204.8A CN201310690204A CN103694414A CN 103694414 A CN103694414 A CN 103694414A CN 201310690204 A CN201310690204 A CN 201310690204A CN 103694414 A CN103694414 A CN 103694414A
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- fluorine
- preparation
- silicon
- fatting agent
- asa
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- 239000010985 leather Substances 0.000 title claims abstract description 39
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 19
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000005576 amination reaction Methods 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- -1 alkenyl succinic anhydride Chemical compound 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229940014800 succinic anhydride Drugs 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Landscapes
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to a preparation method of a fluorine-silicon composite waterproof leather fatliquor. Present waterproof leather fatliquors mostly have the problems of single function, non-ideal general effects and the like. The preparation method comprises the following steps: mixing ASA (alkenyl succinic anhydride), perfluoroalkyl fluoroethanol and a catalyst to react; reducing the temperature and adding an organic silicon coupling agent and an animation reagent to react; and keeping the temperature of the system changeless and adding deionized water to adjust the solid content after adjusting the pH value, thus obtaining the fluorine-silicon composite waterproof leather fatliquor. The preparation method has the beneficial effects that the fluorine-silicon composite waterproof leather fatliquor is modified by using the petroleum byproduct ASA as the main raw material, is low in cost, contains organic fluorine and organic silicon, can enable the leather subjected to fat liquoring to have toughness in softness and elasticity in fullness and simultaneously has good waterproofness, oilproofness and antifouling property; and the preparation method is safe and environment-friendly, is simple in preparation process and is convenient for production.
Description
Technical field
the invention belongs to fine chemicals fabricating technology field, be specifically related to compound leather water-proof fatting agent of a kind of fluorine silicon and preparation method thereof.
Background technology
Leather fat is one of maximum and requisite processing aid of consumption in tanning production, on improving leather quality and performance, has important impact.In order to give the plentiful softness of leather simultaneously, resilient feel and water resistance just need to adopt the fatting agent with good waterproof action in leather processing procedure.
Organic fluorine compounds is the most effective Water-proofing Materials for Leather, and the leather after fluorochemicals is processed has the property such as waterproof, grease proofing, anti-soil, but use easily makes the leather after stuffing harder separately, and feel is bad; Although siliceous fatting agent can improve the flexibility, wear resistance, slipping of leather etc., meanwhile, also, giving leather certain water-repellancy, use separately water-repellancy not ideal.Therefore, comprehensive organic fluorine and organosilyl advantage, prepare the compound leather water-proof fatting agent of a kind of fluorine silicon, can solve prior art and exist the problems such as function singleness, net effect be undesirable.
Summary of the invention
The object of this invention is to provide compound leather water-proof fatting agent of a kind of fluorine silicon and preparation method thereof, to solve the problems such as function singleness that prior art exists and net effect be undesirable.
The technical solution adopted in the present invention is:
A preparation method for the compound leather water-proof fatting agent of fluorine silicon, is characterized in that:
By following steps, realized:
Step 1: by ASA, perfluoroalkyl fluorine alcohol and catalyzer in its weight ratio 1:(0.6～0.9): the ratio hybrid reaction of (0.002～0.005), the condition of its reaction is: 80～150 ℃, the reaction times is 3～5 hours;
Step 2: system temperature is down to 50～70 ℃, in reaction product, add organo-silicon coupling agent and amination reagent to react, the weight ratio of organo-silicon coupling agent, amination reagent and ASA is (0.1～0.2): (0.3～0.4): 1, and the reaction times is 2～3 hours;
Wherein, described organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane;
Step 3: maintenance system is temperature-resistant, adds NaOH solution to regulate pH value to 8～9.5 while stirring; Finally, add deionized water and regulate solid content to 10～20%, obtain the compound leather water-proof fatting agent of a kind of fluorine silicon.
In step 1, perfluoroalkyl fluorine alcohol is selected from perfluor alkyl ethide hexanol, perfluor alkyl ethide octanol or perfluor alkyl ethide decyl alcohol.
In step 1, catalyzer is selected from tosic acid, phosphoric acid or boric acid.
In step 2, amination reagent is selected from diethylamine or triethylamine.
The compound leather water-proof fatting agent of fluorine silicon that the preparation method of the compound leather water-proof fatting agent of a kind of fluorine silicon makes.
The present invention has the following advantages:
(1) effective cost is low: product of the present invention is that main raw material carries out modification with petroleum by-product ASA, with low cost.In molecule, ASA segment has excellent filling stuffing performance, and whole-fluoroalkyl chain segment provides excellent waterproof, grease proofing and antifouling property, and organosilicon coupling improves excellent flexibility, elasticity and toughness.
(2) multi-functional composite synergistic: not only containing organic fluorine but also containing organosilicon, both can make to there is toughness in the leather softness after stuffing, there is elasticity in plentiful, and there is good waterproof, grease proofing and antifouling performance simultaneously.
(3) safety and environmental protection: not containing any organic solvent, take water as dispersion medium when stuffing is used in preparation process, reduced the pollution and harm to environment and operator.
(4) preparation technology is simple: preparation is simple, without particular requirement, is convenient to produce.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail.
The preparation method of the compound leather water-proof fatting agent of a kind of fluorine silicon involved in the present invention, is realized by following steps:
Step 1: by ASA, perfluoroalkyl fluorine alcohol and catalyzer in its weight ratio 1:(0.6～0.9): the ratio hybrid reaction of (0.002～0.005), the condition of its reaction is: 80～150 ℃, the reaction times is 3～5 hours.
Wherein, perfluoroalkyl fluorine alcohol is selected from perfluor alkyl ethide hexanol, perfluor alkyl ethide octanol or perfluor alkyl ethide decyl alcohol;
Catalyzer is selected from tosic acid, phosphoric acid or boric acid.
Step 2: system temperature is down to 50～70 ℃, in reaction product, add organo-silicon coupling agent and amination reagent to react, the weight ratio of organo-silicon coupling agent, amination reagent and ASA is (0.1～0.2): (0.3～0.4): 1, and the reaction times is 2～3 hours.
Wherein, described organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane;
Amination reagent is selected from diethylamine or triethylamine.
Step 3: maintenance system is temperature-resistant, adds NaOH solution to regulate pH value to 8～9.5 while stirring; Finally, add deionized water and regulate solid content to 10～20%, obtain the compound leather water-proof fatting agent of a kind of fluorine silicon.
Alkenyl succinic anhydride (ASA) is the unsaturated hydrocarbon that contains Succinic anhydried side chain on a kind of molecular chain, be alkene and MALEIC ANHYDRIDE generation building-up reactions and product.The carbon chain lengths of general alkene is at C
14-C
20, carbonatoms, more than 20 o'clock, is the thickness amber color liquid of oily at normal temperatures.
Molecular structure is as follows:
Embodiment 1:
Step 1: in the ratio hybrid reaction of its weight ratio 1:0.6:0.002, the condition of its reaction is by ASA, perfluoroalkyl fluorine alcohol and catalyzer: 80 ℃, the reaction times is 3 hours.
Wherein, perfluoroalkyl fluorine alcohol is chosen perfluor alkyl ethide hexanol;
Catalyzer is chosen tosic acid.
Step 2: system temperature is down to 50 ℃, adds organo-silicon coupling agent and amination reagent to react in reaction product, the weight ratio of organo-silicon coupling agent, amination reagent and ASA is 0.1:0.3:1, and the reaction times is 2 hours.
Wherein, described organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane;
Amination reagent is chosen diethylamine.
Step 3: maintenance system is temperature-resistant, adds NaOH solution to regulate pH value to 8 while stirring; Finally, add deionized water and regulate solid content to 10%, obtain the compound leather water-proof fatting agent of a kind of fluorine silicon.
Embodiment 2:
Step 1: in the ratio hybrid reaction of its weight ratio 1:0.7:0.004, the condition of its reaction is by ASA, perfluoroalkyl fluorine alcohol and catalyzer: 115 ℃, the reaction times is 4 hours.
Wherein, perfluoroalkyl fluorine alcohol is chosen perfluor alkyl ethide octanol;
Catalyzer is chosen phosphoric acid.
Step 2: system temperature is down to 60 ℃, adds organo-silicon coupling agent and amination reagent to react in reaction product, the weight ratio of organo-silicon coupling agent, amination reagent and ASA is 0.15:0.35:1, and the reaction times is 2.5 hours.
Wherein, described organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane;
Amination reagent is chosen diethylamine.
Step 3: maintenance system is temperature-resistant, adds NaOH solution to regulate pH value to 9 while stirring; Finally, add deionized water and regulate solid content to 15%, obtain the compound leather water-proof fatting agent of a kind of fluorine silicon.
Embodiment 3:
Step 1: in the ratio hybrid reaction of its weight ratio 1:0.9:0.005, the condition of its reaction is by ASA, perfluoroalkyl fluorine alcohol and catalyzer: 150 ℃, the reaction times is 5 hours.
Wherein, perfluoroalkyl fluorine alcohol is chosen perfluor alkyl ethide decyl alcohol;
Catalyzer is chosen boric acid.
Step 2: system temperature is down to 70 ℃, adds organo-silicon coupling agent and amination reagent to react in reaction product, the weight ratio of organo-silicon coupling agent, amination reagent and ASA is 0.2:0.4:1, and the reaction times is 3 hours.
Wherein, described organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane;
Amination reagent is chosen triethylamine.
Step 3: maintenance system is temperature-resistant, adds NaOH solution to regulate pH value to 9.5 while stirring; Finally, add deionized water and regulate solid content to 20%, obtain the compound leather water-proof fatting agent of a kind of fluorine silicon.
The leather sample specific performance of embodiment 1-3 detects:
Neutralization: put into 4 sheep samples that are numbered 0-3 in 4 rotary drums, neutralize respectively, washing, stuffing technique, wherein, adopt SA synthetic fat liquor (BASF AG), adopt respectively the fatting agent in embodiment 1-3 No. 1-3 for No. 0.
No. 0-4 leather sample carried out to thickness, tensile strength, pliability and water-repellancy and detect, after this waterproof currying agent stuffing, crust leather has good water resistance, and more soft, plentiful, and mechanical property also improves a lot, and concrete detected result is as shown in the table:
It is cited that content of the present invention is not limited to embodiment, and the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification sheets of the present invention, is claim of the present invention and contains.
Claims (5)
1. a preparation method for the compound leather water-proof fatting agent of fluorine silicon, is characterized in that:
By following steps, realized:
Step 1: by ASA, perfluoroalkyl fluorine alcohol and catalyzer in its weight ratio 1:(0.6～0.9): the ratio hybrid reaction of (0.002～0.005), the condition of its reaction is: 80～150 ℃, the reaction times is 3～5 hours;
Step 2: system temperature is down to 50～70 ℃, in reaction product, add organo-silicon coupling agent and amination reagent to react, the weight ratio of organo-silicon coupling agent, amination reagent and ASA is (0.1～0.2): (0.3～0.4): 1, and the reaction times is 2～3 hours;
Wherein, described organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane;
Step 3: maintenance system is temperature-resistant, adds NaOH solution to regulate pH value to 8～9.5 while stirring; Finally, add deionized water and regulate solid content to 10～20%, obtain the compound leather water-proof fatting agent of a kind of fluorine silicon.
2. the preparation method of the compound leather water-proof fatting agent of a kind of fluorine silicon according to claim 1, is characterized in that:
In step 1, perfluoroalkyl fluorine alcohol is selected from perfluor alkyl ethide hexanol, perfluor alkyl ethide octanol or perfluor alkyl ethide decyl alcohol.
3. the preparation method of the compound leather water-proof fatting agent of a kind of fluorine silicon according to claim 2, is characterized in that:
In step 1, catalyzer is selected from tosic acid, phosphoric acid or boric acid.
4. the preparation method of the compound leather water-proof fatting agent of a kind of fluorine silicon according to claim 3, is characterized in that:
In step 2, amination reagent is selected from diethylamine or triethylamine.
5. the compound leather water-proof fatting agent of fluorine silicon being made by the preparation method of the compound leather water-proof fatting agent of a kind of fluorine silicon claimed in claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310690204.8A CN103694414B (en) | 2013-12-17 | 2013-12-17 | A kind of preparation method of fluorine silicon composite waterproof leather fatliquor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310690204.8A CN103694414B (en) | 2013-12-17 | 2013-12-17 | A kind of preparation method of fluorine silicon composite waterproof leather fatliquor |
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| Publication Number | Publication Date |
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| CN103694414A true CN103694414A (en) | 2014-04-02 |
| CN103694414B CN103694414B (en) | 2017-05-31 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107031218A (en) * | 2017-03-21 | 2017-08-11 | 华鸿控股集团有限公司 | A kind of water-resistant type ultraviolet curing glass platinum technique |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693927A (en) * | 2009-10-21 | 2010-04-14 | 陕西科技大学 | Long-chain alkyl alcohol modified ASA waterproof fatliquoring agent and process for preparing same |
| CN101696457A (en) * | 2009-10-21 | 2010-04-21 | 陕西科技大学 | Organic long-chain fluorine-alcohol modified ASA leather waterproof fat liquoring agent and preparation method thereof |
| CN101760967A (en) * | 2008-11-14 | 2010-06-30 | 杨玉生 | Waterproof and oilproof finishing agent for fabric and leather and preparation thereof |
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2013
- 2013-12-17 CN CN201310690204.8A patent/CN103694414B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760967A (en) * | 2008-11-14 | 2010-06-30 | 杨玉生 | Waterproof and oilproof finishing agent for fabric and leather and preparation thereof |
| CN101693927A (en) * | 2009-10-21 | 2010-04-14 | 陕西科技大学 | Long-chain alkyl alcohol modified ASA waterproof fatliquoring agent and process for preparing same |
| CN101696457A (en) * | 2009-10-21 | 2010-04-21 | 陕西科技大学 | Organic long-chain fluorine-alcohol modified ASA leather waterproof fat liquoring agent and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107031218A (en) * | 2017-03-21 | 2017-08-11 | 华鸿控股集团有限公司 | A kind of water-resistant type ultraviolet curing glass platinum technique |
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