CN103694414B - A kind of preparation method of fluorine silicon composite waterproof leather fatliquor - Google Patents
A kind of preparation method of fluorine silicon composite waterproof leather fatliquor Download PDFInfo
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- CN103694414B CN103694414B CN201310690204.8A CN201310690204A CN103694414B CN 103694414 B CN103694414 B CN 103694414B CN 201310690204 A CN201310690204 A CN 201310690204A CN 103694414 B CN103694414 B CN 103694414B
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- composite waterproof
- fluorine
- preparation
- silicon composite
- fluorine silicon
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- 239000010985 leather Substances 0.000 title claims abstract description 38
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000005576 amination reaction Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 19
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 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
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 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
- -1 alkyl ethide Chemical compound 0.000 claims description 4
- 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
- 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
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims 2
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000004078 waterproofing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000012847 fine chemical Substances 0.000 description 1
- 239000004519 grease 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
- 238000000034 method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention relates to a kind of preparation method of fluorine silicon composite waterproof leather fatliquor.There is unitary function, resultant effect mostly in current leather water-proof fatting agent.The present invention is by ASA, perfluoroalkyl fluorine alcohol and catalyst hybrid reaction；Cooling adds organo-silicon coupling agent and amination reagent reaction；Holding system is temperature-resistant, after regulation pH value, plus deionized water regulation solid content, obtain a kind of fluorine silicon composite waterproof leather fatliquor.Present invention petroleum by-product ASA is that primary raw material is modified, with low cost；Not only contained organosilicon again containing Organic fluoride, can both make to have in the softness of the leather after stuffing toughness, it is plentiful in have it is elastic, while having good Water-proof and oil-proof and antifouling performance；Safety and environmental protection, preparation process is simple, be easy to production.
Description
Technical field
The invention belongs to fine chemicals fabricating technology field, and in particular to a kind of compound leather water-proof of fluorine silicon adds
Fat agent and preparation method thereof.
Background technology
Leather fat is one of maximum and essential processing aid of consumption in tanning production, to improving leather quality
There is important influence with performance.In order to while assigning the plentiful softness of leather and resilient feel and water resistance, it is necessary to
Using the fatting agent with good waterproof action in leather processing procedure.
Organic fluoride class compound is maximally effective Water-proofing Materials for Leather, and the leather after being processed through fluorochemical has anti-
The property such as water, grease proofing, anti-soil, but be used alone and easily make that the leather after stuffing is harder, feel is bad；Although siliceous fatting agent can be with
Flexibility, wearability, slipping of leather etc. are improved, meanwhile, also in the water proofing property that imparting leather is certain, but water proofing property is used alone not
It is too preferable.Therefore, the advantage of comprehensive Organic fluoride and organosilicon, prepares a kind of fluorine silicon composite waterproof leather fatliquor, you can solution
Certainly prior art has unitary function, resultant effect.
The content of the invention
It is existing to solve it is an object of the invention to provide a kind of fluorine silicon composite waterproof leather fatliquor and preparation method thereof
The problems such as unitary function and undesirable resultant effect of technology presence.
The technical solution adopted in the present invention is：
A kind of preparation method of fluorine silicon composite waterproof leather fatliquor, it is characterised in that：
Realized by following steps：
Step one：ASA, perfluoroalkyl fluorine alcohol and catalyst are compared 1 by its weight：（0.6~0.9）：（0.002~
0.005）Ratio hybrid reaction, its reaction condition be：80~150 DEG C, the reaction time is 3~5 hours；
Step 2：System temperature is down to 50~70 DEG C, organo-silicon coupling agent and amination reagent are added in the reaction product
Reacted, the weight ratio of organo-silicon coupling agent, amination reagent and ASA is（0.1~0.2）：（0.3~0.4）：1, reaction time
It is 2~3 hours；
Wherein, described organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Step 3：Holding system is temperature-resistant, adds NaOH solution to adjust pH value to 8~9.5 while stirring；Finally, plus
Deionized water adjusts solid content to 10~20%, that is, obtain a kind of fluorine silicon composite waterproof leather fatliquor.
In step one, perfluoroalkyl fluorine alcohol is selected from perfluor alkyl ethide hexanol, perfluor alkyl ethide octanol or perfluoroalkyl
Ethyl decyl alcohol.
In step one, catalyst is selected from p-methyl benzenesulfonic acid, phosphoric acid or boric acid.
In step 2, amination reagent is selected from diethylamine or triethylamine.
Fluorine silicon composite waterproof leather fatliquor obtained in a kind of preparation method of fluorine silicon composite waterproof leather fatliquor.
The present invention has advantages below：
（1）The good low cost of effect：Product petroleum by-product ASA of the present invention is that primary raw material is modified, with low cost.
Intramolecular ASA segments have excellent filling fatliquoring function, and whole-fluoroalkyl chain segment provides excellent Water-proof and oil-proof and soil resistance
Can, organosilicon coupling improves excellent flexibility, elasticity and toughness.
（2）Multi-functional composite synergistic：Not only contained organosilicon again containing Organic fluoride, can both make to have during the leather after stuffing is soft
Toughness, it is plentiful in have elasticity, while having good Water-proof and oil-proof and antifouling performance.
（3）Safety and environmental protection：Any organic solvent is free of in preparation process, with water as decentralized medium when stuffing is used, is subtracted
Pollution and the infringement to environment and operating personnel are lacked.
（4）Preparation process is simple：Preparation is simple, without particular/special requirement, is easy to production.
Specific embodiment
With reference to specific embodiment, the present invention will be described in detail.
A kind of preparation method of fluorine silicon composite waterproof leather fatliquor involved in the present invention, is realized by following steps：
Step one：ASA, perfluoroalkyl fluorine alcohol and catalyst are compared 1 by its weight：（0.6~0.9）：（0.002~
0.005）Ratio hybrid reaction, its reaction condition be：80~150 DEG C, the reaction time 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；
Catalyst is selected from p-methyl benzenesulfonic acid, phosphoric acid or boric acid.
Step 2：System temperature is down to 50~70 DEG C, organo-silicon coupling agent and amination reagent are added in the reaction product
Reacted, the weight ratio of organo-silicon coupling agent, amination reagent and ASA is（0.1~0.2）：（0.3~0.4）：1, reaction time
It 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：Holding system is temperature-resistant, adds NaOH solution to adjust pH value to 8~9.5 while stirring；Finally, plus
Deionized water adjusts solid content to 10~20%, that is, obtain a kind of fluorine silicon composite waterproof leather fatliquor.
Alkenyl succinic anhydride（ASA）It is the unsaturated hydrocarbon containing succinic anhydride side chain on a kind of strand, is
There is product obtained by synthetic reaction with maleic anhydride in alkene.The carbon chain lengths of general alkene are in C14-C20, carbon number
It is at normal temperatures the viscous amber liquid of oily during more than 20.
Molecular structure is as follows：
Embodiment 1：
Step one：ASA, perfluoroalkyl fluorine alcohol and catalyst are compared 1 by its weight：0.6：0.002 ratio hybrid reaction,
Its reaction condition be：80 DEG C, the reaction time is 3 hours.
Wherein, perfluoroalkyl fluorine alcohol chooses perfluor alkyl ethide hexanol；
Catalyst chooses p-methyl benzenesulfonic acid.
Step 2：System temperature is down to 50 DEG C, adds organo-silicon coupling agent and amination reagent to carry out in the reaction product
Reaction, the weight ratio of organo-silicon coupling agent, amination reagent and ASA is 0.1：0.3：1, the reaction time is 2 hours.
Wherein, described organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Amination reagent chooses diethylamine.
Step 3：Holding system is temperature-resistant, adds NaOH solution to adjust pH value to 8 while stirring；Finally, plus deionization
Water adjusts solid content to 10%, that is, obtain a kind of fluorine silicon composite waterproof leather fatliquor.
Embodiment 2：
Step one：ASA, perfluoroalkyl fluorine alcohol and catalyst are compared 1 by its weight：0.7：0.004 ratio hybrid reaction,
Its reaction condition be：115 DEG C, the reaction time is 4 hours.
Wherein, perfluoroalkyl fluorine alcohol chooses perfluor alkyl ethide octanol；
Catalyst chooses phosphoric acid.
Step 2：System temperature is down to 60 DEG C, adds organo-silicon coupling agent and amination reagent to carry out in the reaction product
Reaction, the weight ratio of organo-silicon coupling agent, amination reagent and ASA is 0.15：0.35：1, the reaction time is 2.5 hours.
Wherein, described organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Amination reagent chooses diethylamine.
Step 3：Holding system is temperature-resistant, adds NaOH solution to adjust pH value to 9 while stirring；Finally, plus deionization
Water adjusts solid content to 15%, that is, obtain a kind of fluorine silicon composite waterproof leather fatliquor.
Embodiment 3：
Step one：ASA, perfluoroalkyl fluorine alcohol and catalyst are compared 1 by its weight：0.9：0.005 ratio hybrid reaction,
Its reaction condition be：150 DEG C, the reaction time is 5 hours.
Wherein, perfluoroalkyl fluorine alcohol chooses perfluor alkyl ethide decyl alcohol；
Catalyst chooses boric acid.
Step 2：System temperature is down to 70 DEG C, adds organo-silicon coupling agent and amination reagent to carry out in the reaction product
Reaction, the weight ratio of organo-silicon coupling agent, amination reagent and ASA is 0.2：0.4：1, the reaction time is 3 hours.
Wherein, described organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Amination reagent chooses triethylamine.
Step 3：Holding system is temperature-resistant, adds NaOH solution to adjust pH value to 9.5 while stirring；Finally, plus go from
Sub- water adjusts solid content to 20%, that is, obtain a kind of fluorine silicon composite waterproof leather fatliquor.
The leather sample specific performance detection of embodiment 1-3：
Neutralize：4 pieces of sheep samples that numbering is 0-3 are put into 4 rotary drums, are neutralized respectively, washed, stuffing work
Skill, wherein, No. 0 uses SA synthetic fat liquors（BASF AG）, No. 1-3 fatting agent being respectively adopted in embodiment 1-3.
The detection of thickness, tensile strength, pliability and water proofing property, base after the waterproof currying agent stuffing are carried out to No. 0-4 leather sample
Leather has good water resistance, and more soft, plentiful, and mechanical performance also improves a lot, specific testing result such as following table
It is shown:
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And any equivalent conversion taken technical solution of the present invention, it is claim of the invention and is covered.
Claims (5)
1. a kind of preparation method of fluorine silicon composite waterproof leather fatliquor, it is characterised in that：
Realized by following steps：
Step one：Alkenyl succinic anhydride ASA, perfluoroalkyl fluorine alcohol and catalyst are compared 1 by its weight：（0.6~0.9）：
（0.002~0.005）Ratio hybrid reaction, its reaction condition be：80~150 DEG C, the reaction time is 3~5 hours；
Step 2：System temperature is down to 50~70 DEG C, adds organo-silicon coupling agent and amination reagent to carry out in the reaction product
React, the weight ratio of organo-silicon coupling agent, amination reagent and alkenyl succinic anhydride ASA is（0.1~0.2）：（0.3~0.4）：1,
Reaction time is 2~3 hours；
Wherein, described organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Step 3：Holding system is temperature-resistant, adds NaOH solution to adjust pH value to 8~9.5 while stirring；Finally, plus go from
Sub- water adjusts solid content to 10~20%, that is, obtain a kind of fluorine silicon composite waterproof leather fatliquor.
2. the preparation method of a kind of fluorine silicon composite waterproof leather fatliquor according to claim 1, it is characterised in that：
In step one, 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 a kind of fluorine silicon composite waterproof leather fatliquor according to claim 2, it is characterised in that：
In step one, catalyst is selected from p-methyl benzenesulfonic acid, phosphoric acid or boric acid.
4. the preparation method of a kind of fluorine silicon composite waterproof leather fatliquor according to claim 3, it is characterised in that：
In step 2, amination reagent is selected from diethylamine or triethylamine.
5. the fluorine silicon as obtained in a kind of preparation method of the fluorine silicon composite waterproof leather fatliquor described in claim 4 is compound
Leather water-proof fatting agent.
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| 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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| 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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| CN103694414B true CN103694414B (en) | 2017-05-31 |
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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 |
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