CN106120349B - A kind of environment-friendly type abietyl is without fluoro water proofing agent and preparation method thereof - Google Patents
A kind of environment-friendly type abietyl is without fluoro water proofing agent and preparation method thereof Download PDFInfo
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- CN106120349B CN106120349B CN201610619147.8A CN201610619147A CN106120349B CN 106120349 B CN106120349 B CN 106120349B CN 201610619147 A CN201610619147 A CN 201610619147A CN 106120349 B CN106120349 B CN 106120349B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention relates to a kind of abietyls without fluoro water proofing agent and preparation method thereof, and by weight, the composition of raw materials of the waterproofing agent includes：10 ~ 100 parts of Abietyl modified silicon wax；5 ~ 20 parts of polyether polyurethane resin；5 ~ 20 parts of crosslinking agent；1 ~ 15 part of emulsifier；10 ~ 200 parts of solvent；100 ~ 300 parts of water.The abietyl of the present invention is environment-friendly type waterproofing agent without fluoro water proofing agent, the waterproofing agent avoids the use of fluorine carbon compound, the shortcomings that overcoming dynamic in the prior art without fluoro water proofing agent anti-siphon poor performance, have both the excellent anti-siphon performance of static state, the shortcomings that also overcoming the poor adhesive force of waterproofing agent product and superfine fiber synthetic leather base cloth in the prior art, and the reproducible natural rosin of green is used or derivatives thereof for raw material, with the important value of environmental protection and extremely wide application prospect；And it prepares simple and environmentally-friendly.
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of environment-friendly type abietyl is without fluoro water proofing agent and preparation method thereof.
Background technology
Superfine fiber chemical leather is made of nylon superfine fiber and polyurethane two parts, characteristic and ratio with corium
The superior index of corium.It can compare favourably with advanced natural leather, with the intrinsic sucting wet air permeability of natural leather, both be applicable in
In modernization large-scale production, while again can protecting ecology, reduce environmental pollution, take full advantage of non-natural resource.In its base
In cloth structure, superfine fibre is three-dimensional cross-linked together, plays skeleton and supporting role, forms the knot similar to dermal collagen fiber
Structure.Be distributed in fiber surrounding is polyurethane, it makes entire synthetic leather base cloth form an entirety.However, only drawback is that
Porous structure causes the water proofing property of original base fabric very poor, can overcome this by carrying out water-proofing treatment in dyeing and finishing postfinishing process
One disadvantage.
Fluorochemical acrylate polymer can reduce the surface tension of the base materials such as fabric, paper and leather, can significantly improve
Water repellent/the oil repellent on handled surface, thus had a wide range of applications in the market in current waterproof.However, fluorinated acrylate
Fluorocarbon chain segment structure (C in polymernF2n-1, n is natural number) and it can be degraded into high stability and the carbonization of cumulative fluorine
Object (PFCs) is closed, they can be stabilized for a long time in nature, and have diffusivity higher, have potential hazard to environment
Property.European Union and the U.S. have prohibited the C8 and above fluorocarbons (CnF2n-1, n >=8) and answering in textile finishing field
With therefore, the research and development in recent years in relation to no fluoro water proofing agent become hot spot.Patent CN201610151710.3 discloses wax dispersion
With the compounding of alkyl modified silicon oil without fluoro water proofing agent, the intermiscibility difference of two kinds of components and with the poor adhesive force of base material, therefore simultaneously
It is not suitable for the dynamic water-proof processing of superfine fiber synthetic leather base cloth.
From another point of view, current to be all made of petroleum-based compounds without fluoro water proofing agent be raw material, with petroleum resources
Increasingly depleted and environmental requirement step up, and current chemical industry problem encountered is solved using reproducible natural resources,
With the particularly important value of environmental protection.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of abietyl without fluoro water proofing agent
And preparation method thereof, which has good static and dynamic water-proof in superfine fiber synthetic leather base cloth, overcomes existing
Have in technology without fluoro water proofing agent water proofing property difference and the defects of non-renewable raw material.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of abietyl is without fluoro water proofing agent, and by weight, the composition of raw materials of the waterproofing agent includes：
Further, the general structure of the Abietyl modified silicon wax is as shown in formula I,
Wherein,
R1For C4~C20Branched-chain or straight-chain alkyl；
R2For the substituent group containing rosin ternary phenanthrene ring structure；
R3For the polyethers substituent group containing nitrogen-atoms；
A, b, c, d are natural number, and 10≤a≤50,5≤b≤50,2≤c≤50,20≤d≤200.
In the present invention, R2For-X-NHCO-P, wherein X isOrM, n be less than
Positive integer equal to 10；- CO-P is hydrogenated rosin, rosin or maleic rosin structure substituent group.
Rosin, hydrogenated rosin or maleic rosin etc. contain ternary phenanthrene ring structure, and molecular rigidity is big, easily crystallize, can be notable
Improve the water resistance on accompanying surface.
Preferably ,-the CO-P is hydrogenated rosin or the substituent group of rosin structure.
Further, the X is CH2CH2、CH2CH2CH2、CH2NHCH2、CH2CH2NHCH2CH2、CH2CH2CH2NHCH2CH2
Or CH2CH2CH2NHCH2CH2CH2。
In the present invention, the R3For-R4-NH-CH2-CH(OH)-R5, wherein R4For CH2CH2、CH2CH2CH2、CH2NHCH2、
CH2CH2NHCH2CH2、CH2CH2CH2NHCH2CH2Or CH2CH2CH2NHCH2CH2CH2, R5For polyoxyethylene ether segment, polyoxy third
Alkene ether segment or polyoxyethylene polyoxypropylene base ether segment.
In the present invention, the R1For 1- octyls, 1- dodecyls, 1- myristyls, 1- cetyls, 1- octadecyls or
1- docosyls.
Preferably, the structural formula of the Abietyl modified silicon wax is as shown in formula II,
Wherein, PEO is polyoxyethylene ether segment.
Preferably, the general structure of the PEO is CmH2m-1(CH2CH2O)qCH2, wherein m takes natural number and 1≤m≤6, q
Take natural number and 1≤q≤40.
According to the present invention, the mass content of polyether segment is 50%~80% in the polyether polyurethane resin.This hair
In bright, the polyether polyurethane resin is commercially available, is such as purchased from Jiangsu Hua Da new material Co., Ltd, trade mark DG-
6061, DEG-3751, DG-5130 etc..Also it can make by oneself.
As the polyether polyurethane can be under the action of catalyst prepared by polyethers, isocyanate-monomer.
Wherein, polytetrahydrofuran ether glycol can be selected from by preparing the raw material of the polyethers of above-mentioned polyether polyurethane resin
(PTHF) and/or in the industry such as polyoxypropyleneglycol (PPG) the polyethers raw material being easy to get；
Toluene di-isocyanate(TDI) can be chosen (referred to as by preparing the isocyanate-monomer of above-mentioned polyether polyurethane resin
TDI), oneself two isocyanides of methyl diphenylene diisocyanate (abbreviation MDI), isophorone diisocyanate (abbreviation IPDI), 1,6-
The polyisocyanates such as acid esters (abbreviation HDI) can also choose the dimer or tripolymer of isocyanate-monomer, such as：HDI trimerizations
Body (the Bayer trade mark is DesmodurN3300).
According to the present invention, the crosslinking agent is watersoluble closed type polyurethane curing agent.Such as, Cohan wound waterborne curing agent BL
5140, the aqueous PU curing agent WT-2102 of Bai Situo and win wound Degussa B1358.
According to the present invention, the emulsifier is fatty alcohol polyoxyethylene ether, dodecyl trimethyl ammonium chloride, hexadecane three
One or more combinations in ammonio methacrylate, octadecane trimethyl ammonium chloride (1831).Wherein, fatty alcohol polyoxyethylene ether
MOA-3, MOA-4, MOA-5, MOA-7 and MOA-9 etc. (being purchased from Jiangsu Hai'an petrochemical plant) can be chosen.
According to the present invention, the solvent be methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate,
One or more combinations in methyl amyl acetate.
In the present invention, the preparation method of the Abietyl modified silicon wax includes the following steps：
(1) in the presence of nitrogen protection and six hydration chloroplatinic acids so that alkene and containing hydrogen silicone oil are at 110 DEG C~130 DEG C
At a temperature of react 1~3 hour；
(2) so that step (1) products therefrom in the presence of alkaline matter with amino silicane coupling agent 130 DEG C~150
It is reacted 1~3 hour at DEG C, wherein the amino silicane coupling agent is 3- aminopropyltriethoxies diethoxy silane, 3- aminopropyl first
Base dimethoxysilane, N- (2- aminoethyls) -3- aminopropyltriethoxies diethoxy silane, N- (2- aminoethyls) -3- aminopropyl first
One or more combinations in base dimethoxysilane；
(3) so that step (2) products therefrom reacts 1~3 hour with rosin based material at a temperature of 130 DEG C~150 DEG C,
In, the rosin based material is one or more combinations in rosin, hydrogenated rosin, maleic rosin；
(4) it so that step (3) products therefrom reacts 1~3 hour with ether compound at a temperature of 130 DEG C~150 DEG C, makes
It is standby to obtain the Abietyl modified silicon wax, wherein the ether compound is monocycle oxygroup end-capped polyoxyethylene base ether, monocycle oxygroup
Block one kind of multiple combinations in polyoxypropylene base ether, monocycle oxygroup end-capped polyoxyethylene polyoxypropylene base ether.
Further, in step (1), it is described six hydration chloroplatinic acid be mass concentration be 1%~5%, solvent is that methyl is different
Six hydration platinum acid chloride solutions of acetone；For the feed postition of containing hydrogen silicone oil by the way of being added dropwise, time for adding is in 4 hours；Platinum
Mass content of the element in overall reaction material is 5~20ppm, functional group CH=CH in raw material2It is equimolar ratio with Si-H.
Specifically, the specific implementation mode of step (1) is as follows：Under nitrogen protection, by 5%~15% alkene and 0.1%
~0.3% six hydration platinum acid chloride solution is uniformly mixed, 10%~20% containing hydrogen silicone oil of dropwise addition at a temperature of 110 DEG C~130 DEG C, and 4
It is added dropwise in hour and reacts 1~3 hour at this temperature, obtain reaction solution 1, reaction solution 1 is directly used in anti-in next step
It answers.
The specific implementation mode of step (2) is as follows：After reaction solution 1 obtained by step (1) is cooled to 70 DEG C~90 DEG C, it is added
10%~25% amino silicane coupling agent and 5%~10% sodium hydrate aqueous solution, it is then anti-at 130 DEG C~150 temperature DEG C
It answers 1~3 hour, then takes off low boiling 1~3 hour in the vacuum under pressure of 3~6kPa, obtain reaction solution 2, reaction solution 2 is direct
For reacting in next step.
Preferably, in step (2), the heating-up time that temperature is warming up to 130 DEG C~150 DEG C from 70 DEG C~90 DEG C is 1~3 small
When；The mass concentration of sodium hydrate aqueous solution is 4%~8%.
The specific implementation mode of step (3) is as follows：10%~30% rosin is added in reaction solution 2 obtained by step (2)
Substance reacts 1~3 hour at a temperature of 130 DEG C~150 DEG C, it is small then to take off low boiling 1~3 in the vacuum under pressure of 3~6kPa
When, reaction solution 3 is obtained, reaction solution 3 is directly used in and is reacted in next step.
The specific implementation mode of step (4) is as follows：After reaction solution 3 obtained by step (3) is cooled to 70 DEG C~90 DEG C, it is added
Then 10%~35% ether compound reacts 1~3 hour at 130 DEG C~150 DEG C, then true under the pressure of 3~6kPa
The de- low boiling of sky 1~3 hour, is prepared the Abietyl modified silicon wax.
Preferably, in step (4), the heating-up time that temperature is warming up to 130 DEG C~150 DEG C from 70 DEG C~90 DEG C is 1~3 small
When.
Above-mentioned percentage composition is in terms of mass percentage.
Preferably, the resinous compounds are hydrogenated rosin.
Preferably, the pressure is 5kPa.
In the present invention, raw material described in whole can not have by commercially available and/or take known means and be prepared
When being illustrated, it is satisfied by the requirement of standard chemical products.
The present invention takes another technical solution：A kind of preparation method of the above-mentioned abietyl without fluoro water proofing agent, the preparation
Method is：By formula, first Abietyl modified silicon wax and stirring solvent are uniformly mixed, polyether polyurethane resin, breast is then added
Agent and water, are uniformly mixed, and crosslinking agent is then added at ambient temperature, are stirred reaction, after the completion of reaction to obtain the final product
The abietyl is without fluoro water proofing agent.
Due to the implementation of above-mentioned technical proposal, the present invention has the following advantages that compared with prior art：
The waterproofing agent of the present invention improves handled surface by introducing rosin and its derivative in the side chain of organosilicon
Water proofing property, while the utilization rate of natural reproducible compound is improved, alleviate dependence of the mankind to fossil resource to a certain extent；
By introducing hydrophobic group (chain alkyl) and hydrophilic radical (nitrogenous polyethers) in the side chain of organosilicon, while improving anti-
Aqueous energy and adhesive force, it is final to realize static and dynamic water-proof performance promotion；By the way that aqueous polyurethane tree is added in formula
Fat and crosslinking agent, to further increase above-mentioned adhesive force.
The abietyl of the present invention is environment-friendly type waterproofing agent without fluoro water proofing agent, which avoids making for fluorine carbon compound
With the shortcomings that overcoming dynamic in the prior art without fluoro water proofing agent anti-siphon poor performance, having both the excellent anti-siphon of static state
Can, the shortcomings that also overcoming the poor adhesive force of waterproofing agent product and superfine fiber synthetic leather base cloth in the prior art, and use
Reproducible natural rosin of green or derivatives thereof is raw material, has the important value of environmental protection and extremely wide application prospect；
And it prepares simple and environmentally-friendly.
Description of the drawings
Fig. 1 is the nuclear-magnetism H of the SW-1 of embodiment 11NMR analysis of spectra.
Specific implementation mode
With reference to specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following implementations
Example.
Embodiment 1
The preparation of Abietyl modified silicon wax (SW-1), shown in the structural formula meeting formula II of SW-1, wherein a=20, b=20, c
=20, d=60, n=15.
Preparation method is as follows：
Under nitrogen protection, 20g 1- hexadecylenes and 0.2g six are hydrated platinum acid chloride solution (mass concentration 1%, solvent
For methyl isopropyl ketone) it is uniformly mixed, 26.5g containing hydrogen silicone oils (hydrogen content 0.34%) are slowly added to after being warming up to 120 DEG C, 4 is small
When interior be added dropwise and continue insulation reaction 2 hours；After being cooled to 80 DEG C, 31.9g γ-aminopropyltriethoxy diethoxy silicon is added
Alkane and 10g sodium hydrate aqueous solutions (mass concentration 5%), 140 DEG C are to slowly warm up within 2 hours, continues to be stirred to react 2
Hour, finally low boiling is taken off in the vacuum under pressure of 5kPa obtain amino modified silicon wax product in 2 hours；Slowly add in nitrogen atmosphere
Enter 26.9g hydrogenated rosin powder, insulation reaction 2 hours at 140 DEG C take off low boiling 2 hours in the vacuum under pressure of 5kPa；It will be upper
It states after product material is cooled to 80 DEG C, 44.5g monocycle oxygroup end-capped polyoxyethylene base ethers (molecular weight 500g/mol) is added,
It is to slowly warm up to 140 DEG C within 2 hours, continues insulation reaction 2 hours, finally takes off low boiling 2 hours in the vacuum under pressure of 5kPa
Obtain Abietyl modified silicon wax.
Among the above, monocycle oxygroup end-capped polyoxyethylene base ether is purchased from Hangzhou Dan Wei Science and Technology Ltd.s, trade mark DEG-
501。
Embodiment 2
The preparation of Abietyl modified silicon wax (SW-2), shown in the structural formula meeting formula II of SW-2, wherein a=20, b=20, c
=20, d=60, n=17.
According to preparation method shown in embodiment 1, raw material 1- hexadecylenes are changed into 1- octadecylenes, corrresponding quality becomes
22.5g, other are the same as embodiment 1.
Embodiment 3
The preparation of Abietyl modified silicon wax (SW-3), shown in the structural formula meeting formula II of SW-3, wherein a=20, b=30, c
=10, d=60, n=15.
According to preparation method shown in embodiment 1, the quality of raw material monocycle oxygroup end-capped polyoxyethylene base ether is become
The quality of 22.2g, hydrogenated rosin become 40.4g, other are the same as embodiment 1.
Embodiment 4
The preparation of polyether polyurethane resin (W-PU), preparation method are：(referred to as by 200g polyoxypropyleneglycols
PPG, molecular weight are 400g/mol) stirring dehydration 0.5 hour at 50 DEG C；80 DEG C are gradually heating to, 0.5g tin dilaurates are added
Dibutyl tin is gradually added into 100g isophorone diisocyanate under nitrogen protection, and feeding in 2 hours finishes, and continues to keep the temperature
Reaction 2 hours.
Comparative example 1
The preparation of polyether-modified silicon wax (MW-1), shown in the structural formula meeting formula II of MW-1, wherein a=20, b=0, c=
20, d=60, n=15.
According to preparation method shown in embodiment 1, the quality of raw material γ-aminopropyltriethoxy diethoxy silane is changed to
16.0g does not use hydrogenated rosin, remaining is the same as embodiment 1.
Comparative example 2
The preparation of ordinary silicon wax (MW-2), shown in the structural formula meeting formula II of MW-2, wherein a=20, b=0, c=0, d
=60, n=15.
According to preparation method shown in embodiment 1, without using raw material γ-aminopropyltriethoxy diethoxy silane, monocycle oxygen
Base end-capped polyoxyethylene base ether and hydrogenated rosin, remaining is the same as embodiment 1.
Nuclear-magnetism H is carried out to the SW-1 compounds of embodiment 11NMR is analyzed, the H of SW-11NMR analysis results as shown in Figure 1, by
Known to Fig. 1：Near 0ppm, 0.8~2.1ppm, 2.6ppm, 3.5ppm there is displacement peak, wherein 0ppm has nearby been belonged to
The side group Si-CH of machine silicon chain3In chemical shift of proton peak；0.8~2.1ppm belongs to the ternary phenanthrene ring of hydrogenated rosin, amine third
Base Si-CH2CH2, cetyl C16H33With the chemical shift of proton peak in end alkyl in polyoxy vinyl ethers；2.6ppm returning
Belong to the amine propyl Si-CH of organosilicon side chain2CH2CH2The methylene CH being connected directly with amido bond in NH-CO2Protonate degree
Move peak；3.5ppm belongs to polyoxyethylene ether CH2CH2Chemical shift of proton peak in O.
Nuclear-magnetism H is carried out to the MW-1 compounds of comparative example 11NMR is analyzed, the H of MW-11NMR analysis results are as follows：In 0ppm
Nearby, there is displacement peak in 1ppm, 1.1~1.5ppm, 2.6ppm, 3.5ppm, wherein 0ppm nearby belongs to the side of organosilicon chain
Base Si-CH3In chemical shift of proton peak；1ppm belongs to cetyl C16H33In end alkyl in polyoxy vinyl ethers
- CH3Chemical shift of proton peak；1.1~1.5ppm belongs to amine propyl Si-CH2CH2, cetyl C16H33With polyoxy second
The chemical shift of proton peak of end alkyl in alkene ether；2.6ppm belongs to the amine propyl Si-CH of organosilicon side chain2CH2CH2NH-
The methylene CH being connected directly with amido bond in CO2Chemical shift of proton peak；3.5ppm belongs to polyoxyethylene ether CH2CH2O
In chemical shift of proton peak.
Nuclear-magnetism H is carried out to the MW-2 compounds of comparative example 21NMR is analyzed, the H of MW-21NMR analysis results are as follows：In 0ppm
Nearby, there is displacement peak in 1ppm, 1.30ppm, 2.6ppm, 3.5ppm, wherein 0ppm nearby belongs to the side group of organosilicon chain
Si-CH3In chemical shift of proton peak；1ppm belongs to cetyl C16H33- the CH of end3Chemical shift of proton peak；
1.30ppm belongs to cetyl C16H33In methylene CH2Chemical shift of proton peak；2.6ppm belongs to organosilicon side chain
Amine propyl Si-CH2CH2CH2The methylene CH being connected directly with amido bond in NH-CO2Chemical shift of proton peak；3.5ppm returning
Belong to polyoxyethylene ether CH2CH2Chemical shift of proton peak in O.
It is compared by the nuclear magnetic spectrogram of SW-1, MW-1 and MW-2, it can be seen that hydrogenated rosin, cetyl and polyoxyethylene
Base ether successfully grafts in organosilicon chain.
The preparation of waterproofing agent
The product that above-described embodiment 1~4 and comparative example 1~2 are prepared is used to prepare waterproofing agent, waterproof is prepared
Agent sample 1,2,3,4 and 5, the formula of waterproofing agent sample 1~5 is as shown in table 1, and the preparation of waterproofing agent includes the following steps：
(1) Abietyl modified silicon wax (or silicon wax) and solvent are added in high speed dispersor and stir into clear solution；
(2) after being blended, polyether polyurethane resin, emulsifier and water is added, through high-speed stirred and is cooled to room temperature；
(3) crosslinking agent is added, is stirred, dispenses to get waterproofing agent.
Polythene wax emulsion HA-soft80 has been used (to be purchased from Jiangsu Hai'an petrochemical industry in the formula of waterproofing agent sample 5
Factory, trade mark HA-soft80)) component crosslinking agent and polyether polyurethane resin are substituted, then compounded with Organosilicon wax.
Performance test methods
1, static anti-siphon performance test methods
White superfine fiber synthetic leather base cloth is cut into 10cm × 20cm sizes, is placed in constant temperature and humidity incubator,
The damping 12h under conditions of 23 ± 1 DEG C of temperature, humidity 50 ± 2%；Weighing 16.0g waterproofing agent samples adds tap water to be diluted to
400g is stirred evenly spare；Woven fabric leather base cloth is placed in fabric finishing agent test solution and impregnates 20s, then passes through roller mill
It squeezes, repetition is padded once, is baked 3 minutes in 170 DEG C of baking ovens, and taking-up is placed in get damp again 3 minutes at room temperature；After baking super
It is drawn a straight line at 2cm in fine leather base cloth as label, woven fabric leather base cloth vertical hanging and immerses red ink solution (red ink
Mass content be 50%) at 2cm；It stands and is taken out after placing 72h, blot surface ink and tried in 120 DEG C of drying in oven
Piece cuts off the climb altitude of base fabric observation red ink.
2, the anti-siphon performance test methods of dynamic
The dynamic water-proof performance of superfine fiber synthetic leather base cloth, the following institute of specific operation process are tested with reference to Maeser methods
Show：
The white superfine fiber synthetic leather base cloth that size is 500 × 120mm is placed in constant temperature and humidity incubator, in temperature
23 ± 1 DEG C of degree, damping 12h under conditions of humidity 50 ± 2%；Weighing 32g waterproofing agent samples adds tap water to be diluted to 800g, stirring
It is uniformly spare；Monoblock woven fabric leather base cloth is placed in fabric finishing agent test solution and impregnates 30s, is then squeezed by roller mill,
Repetition is padded once, is baked 3 minutes in 170 DEG C of baking ovens, and taking-up is placed in get damp again 3 minutes at room temperature；White superfine fibre is closed
101.6 × 101.6 ± 3.2mm sizes are cut at leather base cloth, amount to 4 pieces；Test piece is installed on MAESER leather dynamic water-proofs
On testing machine, 135 ± 5g steel balls are placed in test piece groove lining, machine is opened and counts.
Table 1 is the composition of raw materials and the performance test results of sample 1~5
Compounding it can be seen from the comparison of sample 1~4 in table 1 and sample 5 with common Organosilicon wax and polyvinyl wax
System is compared, and Abietyl modified silicon wax and polyether polyurethane compound system have significant static and dynamic water-proof performance advantage；
Can be seen that rosin from the comparison of sample 1~4 can significantly improve static anti-siphon performance, and then too high levels can influence to move
The anti-siphon performance of state, therefore the content of rosin is unsuitable excessively high；It can be seen that from the comparison of sample 1~3 and have by raw material of octadecylene
There is the anti-siphon performance of excellent dynamic.
The present invention is described in detail above, its object is to allow the personage for being familiar with this field technology that can understand this
The content of invention is simultaneously implemented, and it is not intended to limit the scope of the present invention, and the present invention is not limited to above-mentioned implementations
, equivalent change or modification made by all Spirit Essences according to the present invention should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of abietyl is without fluoro water proofing agent, it is characterised in that：By weight, the composition of raw materials of the waterproofing agent includes：
The general structure of the Abietyl modified silicon wax as shown in formula I,
Wherein,
R1For C4~C20Branched-chain or straight-chain alkyl；
R2For the substituent group containing rosin ternary phenanthrene ring structure；
R3For the polyethers substituent group containing nitrogen-atoms；
A, b, c, d are natural number, and 10≤a≤50,5≤b≤50,2≤c≤50,20≤d≤200；
The solvent is in methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl amyl acetate
One or more combinations.
2. abietyl according to claim 1 is without fluoro water proofing agent, it is characterised in that：R2For-X-NHCO-P, wherein X isE, p is the positive integer less than or equal to 10；- CO-P is hydrogenated rosin, rosin or horse
Carry out rosin structure substituent group.
3. abietyl according to claim 2 is without fluoro water proofing agent, it is characterised in that：The X is CH2CH2、CH2CH2CH2、
CH2NHCH2、CH2CH2NHCH2CH2、CH2CH2CH2NHCH2CH2Or CH2CH2CH2NHCH2CH2CH2。
4. abietyl according to claim 1 is without fluoro water proofing agent, it is characterised in that：The R3For-R4-NH-CH2-CH
(OH)-R5, wherein R4For CH2CH2、CH2CH2CH2、CH2NHCH2、CH2CH2NHCH2CH2、CH2CH2CH2NHCH2CH2Or
CH2CH2CH2NHCH2CH2CH2, R5For polyoxyethylene ether segment, polyoxypropylene base ether segment or polyoxyethylene polyoxypropylene base
Ether segment.
5. abietyl according to claim 1 is without fluoro water proofing agent, it is characterised in that：The structural formula of the Abietyl modified silicon wax
As shown in formula II,
Wherein, PEO is polyoxyethylene ether segment, 3≤n≤19.
6. abietyl according to claim 1 is without fluoro water proofing agent, it is characterised in that：Gather in the polyether polyurethane resin
The mass content of ether segment is 50%~80%.
7. abietyl according to claim 1 is without fluoro water proofing agent, it is characterised in that：The crosslinking agent is poly- for watersoluble closed type
Urethane curing agent.
8. abietyl according to claim 1 is without fluoro water proofing agent, it is characterised in that：The emulsifier is fatty alcohol polyoxy second
It is one or more in alkene ether, dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecane trimethyl ammonium chloride
Combination.
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|---|---|---|---|---|
| EP1772552A2 (en) * | 2006-07-20 | 2007-04-11 | Singtex Industrial Co., Ltd. | Porous polytetrafluoroethylene membrane treated with an anti-staining and anti-peeling agent |
| CN102250358A (en) * | 2011-05-18 | 2011-11-23 | 黄山市强力化工有限公司 | Block type amino polyether modified silicone oil and preparation method thereof |
| CN102617859A (en) * | 2012-04-17 | 2012-08-01 | 江西省科学院应用化学研究所 | Method for preparing rosin modified organic silicon resin |
| CN103724561A (en) * | 2013-11-08 | 2014-04-16 | 绍兴鼎翔纺织品贸易有限公司 | Preparation method of hydrophilic modified amino silicone oil |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1772552A2 (en) * | 2006-07-20 | 2007-04-11 | Singtex Industrial Co., Ltd. | Porous polytetrafluoroethylene membrane treated with an anti-staining and anti-peeling agent |
| CN102250358A (en) * | 2011-05-18 | 2011-11-23 | 黄山市强力化工有限公司 | Block type amino polyether modified silicone oil and preparation method thereof |
| CN102617859A (en) * | 2012-04-17 | 2012-08-01 | 江西省科学院应用化学研究所 | Method for preparing rosin modified organic silicon resin |
| CN103724561A (en) * | 2013-11-08 | 2014-04-16 | 绍兴鼎翔纺织品贸易有限公司 | Preparation method of hydrophilic modified amino silicone oil |
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