CN105603755A - Washable fluoride-free waterproof composition - Google Patents
Washable fluoride-free waterproof composition Download PDFInfo
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- CN105603755A CN105603755A CN201410673454.5A CN201410673454A CN105603755A CN 105603755 A CN105603755 A CN 105603755A CN 201410673454 A CN201410673454 A CN 201410673454A CN 105603755 A CN105603755 A CN 105603755A
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Abstract
The invention discloses a washable fluoride-free waterproof composition. The washable fluoride-free waterproof composition comprises the following components by weight percentage: 25-60% of a compound A, 15-40% of an acrylate polymer, 3-40% of an emulsifier, and the balance of water. The washable fluoride-free waterproof composition provides excellent waterproof effect for the fabrics, and provides good washing-resistant performance.
Description
Technical field
The present invention relates to a kind of composition, particularly relate to a kind of water-fastness floride-free water-proofing composition.
Background technology
Along with the raising of people's living standard, people are more and more higher to the requirement of fabric functional, for example there are non-ironing, antibacterial, soft, fire-retardant or water-proof function etc., wherein water-proof function arrangement aspect, especially best with the waterproof effect of fluorine-contaninig polyacrylate emulsion or solution, because the fabric after wherethrough reason or base material have extremely low surface energy, water is difficult at its moistened surface. And fluorinated polyacrylic acid is especially best with the effect of contain-C8F17 group, be that people are conventionally referred to as C8 class waterproofing agent, but C8 class waterproofing agent is because contain micro-perfluorooctanoic acid harmful substance or easily cause producing perfluorooctanoic acid material and suffer European Union, restriction application or the forbidding of the U.S. and other developed country, determine to stop the production of C8 product to the 2012 main collectives of C8 Fu Tan waterproofing agent supplier in the whole world in the end of the year, will thoroughly stop the sale of C8 product to the end of the year 2015. Therefore increasing enterprise starts to turn to the substitute of C8. 2010 Chinese patent (application number is 201080009570.7) a kind of waterproofing agent is disclosed, comprise acrylate polymer and paraffin etc. This patent has been used a large amount of paraffin as main waterproof thing, because paraffin is poor to the compatibility of fiber or fabric, therefore initial waterproof effect is restricted. 2014 Chinese patent (application number is 201310505871.4) a kind of waterproofing agent is disclosed, comprise acrylate polymer and Tissuemat E etc. Although this patent has been used Tissuemat E that compatibility is slightly good as main waterproof thing, for example hydroxyl of the polar group in Tissuemat E or carboxyl, make its initial waterproof effect also receive certain impact.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of water-fastness floride-free water-proofing composition, and it can give fabric outstanding waterproof effect, can give again its good water-wash resistance.
The present invention solves above-mentioned technical problem by following technical proposals: a kind of water-fastness floride-free water-proofing composition, it is characterized in that, and its component is as follows, by weight percentage: the compd A of 25-60%; The acrylate polymer of 15-40%; The emulsifying agent of 3-40%; Other is water.
Preferably, described chemical combination A is synthetic by fatty alcohol or the fatty amine of isocyanates and long-chain.
Preferably, the fatty alcohol of described long-chain is direct-connected or the aliphatic alcohol that contains side chain, to represent with structural formula below:
Wherein, R1, R2, R3 can be with representing that formula X-Y-Z or Z represent:
X is with representing Shi – (CH2) t-represents, t=0-30;
Y with represent Shi-O-C (O)-or-O-C (O)-NH-represents;
Z is with representing Shi – (CH2)m-HRepresent m=0-30;
Wherein, R4Can be with representing Shi – (CH2)p-(OCH2CH2)q-(OCH2CH(CH3))r-OH represents, p, q and r=0-30.
Preferably, the fatty amine of described long-chain is direct-connected or the aliphatic amine that contains side chain, represents with structural formula below:
Wherein, n=0-2; Q can be with representing Shi-(CH2) y-represents, y=1-4; B4Be H or
–(CH2)f-H，f=0-30；B1，B2，B3Can be with representing that formula V-W-U or U represent:
V is with representing Shi – (CH2)d-represent d=0-30;
W with represent Shi-O-C (O)-or-O-C (O)-NH-represents;
U is with representing Shi – (CH2)e-H represents, e=0-30.
Preferably, described isocyanates be end-blocking or end-blocking not, degree of functionality is between 1.8-5.
Preferably, the mol ratio of the fatty alcohol of described long-chain or fatty amine and isocyanates is that 1:10 is to 1:1.3.
Preferably, described acrylate polymer is the copolymer of construction unit composition below: by weight percentage, and the acrylate or the methacrylate that contain 10 to 24 carbon atoms of 25-60%, or the mixture of acrylate and methacrylate; 10% to 40% vinylidene chloride; 10% to 40% the acrylate that contains functional group or methacrylate, or the mixture of acrylate and methacrylate; 0.0001% to 0.1% initator.
Preferably, described in contain 10 to 24 carbon atoms acrylate or methacrylate be side chain, or be also straight chain or ring-type.
Preferably, described functional group refers to and contains hydroxyl, or epoxy radicals, or amide groups, or carboxyl, or alkoxyl, or the NCO of sealing.
Preferably, described initator refers to the initiator system of one or several or redox class in water miscible a kind of persulfuric acid salt or azo.
Preferably, described emulsifying agent is nonionic emulsifier or anion emulsifier or cationic emulsifier or nonionic and anion or cationic mixture.
Positive progressive effect of the present invention is: the present invention can give fabric outstanding waterproof effect, can give again its good water-wash resistance. Compared with prior art, main water repellent component compd A disclosed in this invention be branchedization with many alkyl, multiple hydrophobic groupings concentrate on a molecule, make it refuse water effect and greatly strengthen; In addition the urea key in compd A molecule is relatively good to the affinity of fiber or fabric, does not affect again waterproof effect, and therefore more traditional paraffin or Tissuemat E class are all good without waterproof effect and the washability of fluoro water proofing agent.
Detailed description of the invention
The component of water-proofing composition provided by the invention is as follows, by weight percentage: the compd A of 10-90%; The acrylate polymer of 10-90%; Appropriate emulsifying agent; Other is water.
The preparation process of water-fastness floride-free water-proofing composition is as follows: by compd A, acrylate monomer, emulsifying agent and water, stir and obtain pre-emulsion in high speed shear, then after logical nitrogen deoxygenation, add initator and vinylidene chloride, be warming up to 30-90 degree Celsius, insulation reaction 4-20 hour, filters discharging.
Wherein, compd A is synthetic by fatty alcohol or the fatty amine of isocyanates and long-chain.
The technical process of preparing compd A is as follows: after the fatty alcohol of solvent, isocyanates and long-chain or fatty amine are mixed, be heated to the temperature of appointment, after insulation reaction 5-20 hour, solvent decompression removed to rear discharging.
Wherein, the fatty alcohol of long-chain can be direct-connected or the aliphatic alcohol that contains side chain, can be to represent with structural formula (1) below:
…………………………………………………（1）
Wherein, R1, R2, R3 can be with representing that formula X-Y-Z or Z represent:
X can be with representing Shi – (CH2) t-represents, t=0-30;
Y can with represent Shi-O-C (O)-or-O-C (O)-NH-represents;
Z can be with representing Shi – (CH2)m-HRepresent m=0-30;
Wherein, R4Can be with representing Shi – (CH2)p-(OCH2CH2)q-(OCH2CH(CH3))r-OH represents, p, q and r=0-30.
Wherein, the fatty amine of long-chain can be direct-connected or the aliphatic amine that contains side chain, can represent with structural formula (2) below:
………………………………………………（2）
Wherein, n=0-2; Q can be with representing Shi-(CH2) y-represents, y=1-4; B4Be H or
–(CH2)f-H，f=0-30；B1，B2，B3Can be with representing that formula V-W-U or U represent:
V can be with representing Shi – (CH2)d-represent d=0-30;
W can with represent Shi-O-C (O)-or-O-C (O)-NH-represents;
U can be with representing Shi – (CH2)e-H represents, e=0-30.
Wherein, isocyanates can be end-blocking or end-blocking not, degree of functionality is between 1.8-5, preferably degree of functionality is between 2-4. The mol ratio of the fatty alcohol of long-chain or fatty amine and isocyanates is that 1:10 is to 1:1.3.
Wherein, preparing the needed solvent of compd A by isocyanates and fatty alcohol or fatty amine can be that ketone comprises aliphatic ketone, alicyclic ketone, aromatic ketone, saturated ketone and beta-unsaturated ketone such as acetone, methyl ethyl ketone, pentanone, propiophenone etc.; Also can be that ester class comprises inorganic acid ester and organic acid esters for example methyl-hydrogen-sulfate monomethyl-sulfate, ethyl acetate, isopropyl acetate, butyl acetate; Can be such as toluene, dimethylbenzene etc. of aromatic hydrocarbon; Halogenated hydrocarbons is carrene, chloroform and tetrachloromethane etc. such as.
Wherein, prepare the needed reaction temperature of compd A at 50-120 degree Celsius by isocyanates and fatty alcohol or fatty amine.
Wherein, acrylate polymer is the copolymer of construction unit composition below: by weight percentage, and the acrylate or the methacrylate that contain 10 to 24 carbon atoms of 25-60%, or the mixture of acrylate and methacrylate; 10% to 40% vinylidene chloride; 10% to 40% the acrylate that contains functional group or methacrylate, or the mixture of acrylate and methacrylate; 0.0001% to 0.1% initator.
The acrylate that contains 10 to 24 carbon atoms or methacrylate can be side chains, can be also straight chain or ring-type, preferably straight chain.
Wherein, functional group refers to and contains hydroxyl, or epoxy radicals, or amide groups, or carboxyl, or alkoxyl, or the NCO of sealing. Preferably, functional monomer is selected from one or more in acrylamide, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, acrylic acid glycidol ether, methyl propenoic acid glycidyl ether, vinyltrimethoxy silane, 3-chlorine-2-hydroxyl-propyl methacrylate and DAAM.
Wherein, initator refers to the initiator system of one or several or redox class in water miscible a kind of persulfuric acid salt or azo. Preferably azo diisobutyl amidine hydrochloride (AIBA, V-50 initator), azo two isobutyl imidazoline salt hydrochlorates (are called for short AIBA, VA-044 initator), azo dicyano valeric acid (being called for short ACVA, V-501), azo diisopropyl imidazoline (being called for short AIP, VA-061 initator).
Emulsifying agent may be, but not limited to,, and is nonionic emulsifier or anion emulsifier or cationic emulsifier or nonionic and anion or cationic mixture. Mentioned emulsifier can be used alone or as the combination of two or more kinds. But get rid of anion and cationic combination. Specifically, emulsifying agent can be nonionic emulsifier, as polyoxyethylene alkyl ether, and polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, fatty acid glyceride etc.; Anion emulsifier, as lauryl sodium sulfate, neopelex, Dodecyl Polyoxyethylene Ether carboxylic acid etc.; Cationic emulsifier, as tallow base trimethyl ammonium chloride quaternary ammonium, hexadecyltrimethylammonium chloride, dioctadecyl dimethyl ammonium chloride and ethoxylation hydrogenation ox ester group alkyl dimethyl ammonium chloride etc. Mentioned emulsifier can be used alone or uses as the combination of two or more kinds. But get rid of anion and cationic combination. Preferably, cation or cation and non-ionic composition. The consumption of emulsifying agent is 0.001% to 10%, preferably, is 0.1% to 3% of percentage by weight.
Polymerization temperature, can be in the scope of 30-90 degree Celsius, preferably at 50-70 degree Celsius according to the kind difference of initator.
Embodiment 1
Compd A synthetic: the dibutyl tin laurate of 156.0g glycerol-1,3-dipalmitate, 53.1gHDI tripolymer (21.8%NCO), 209.0g isopropyl acetate and catalytic amount reacts until with the existence of can't detect-NCO of infrared spectrum group under 80 degrees Celsius.
Embodiment 2
Compd A synthetic: the dibutyl tin laurate of addition product (13.5%NCO), 181.0g isopropyl acetate and the catalytic amount of 141.0g distearyl triethylenetetraminehexaacetic acid hydramine diester, 40.1gTDI and trihydroxymethyl propane react until with the existence of can't detect-NCO of infrared spectrum group, solvent is reduced pressure and removes rear discharging under 70 degrees Celsius.
Embodiment 3
Compd A synthetic: the dibutyl tin laurate of addition product (13.5%NCO), 242.0g isopropyl acetate and the catalytic amount of 156.0g glycerol-1,3-dipalmitate, 85.7gTDI and trihydroxymethyl propane react until with the existence of can't detect-NCO of infrared spectrum group, solvent is reduced pressure and removes rear discharging under 65 degrees Celsius.
Embodiment 4
Compd A synthetic: the dibutyl tin laurate of 141.0g distearyl triethylenetetraminehexaacetic acid hydramine diester, 24.8g1gHDI tripolymer (21.8%NCO), 171.0g isopropyl acetate and catalytic amount react until with the existence of can't detect-NCO of infrared spectrum group, solvent is reduced pressure and removes rear discharging under 60 degrees Celsius.
The synthetic of floride-free water-proofing composition given an example:
Embodiment 5
Synthesizing of water-proofing composition: the compd A in the hydroxy-ethyl acrylate of 150.0g octadecyl acrylate, 5.0g, 200.0g embodiment 1,30.0gTergitol15-s-15 (DOW Chemical product), 3.0g hexadecyltrimethylammonium chloride and 760.0g deionized water are heated to 50 degrees Celsius of high speed shear stirrings and obtain the pre-emulsion that particle diameter is less than 100nm, then logical nitrogen deoxygenation adds azo-bis-isobutyrate hydrochloride and the 55.0g vinylidene chloride of 0.2g after 30 minutes, be warming up to 55-65 degree Celsius, after insulation reaction 10 hours, filter discharging.
Embodiment 6
Synthesizing of floride-free water-proofing composition: by 150.0g acrylic acid mountain Yu base ester, the hydroxyethyl methacrylate of 1.0g, compd A in 200.0g embodiment 2, 40.0gMultiso13-120(isomery alcohol APEO, husky rope product), 3.0gEthoquadHT25(ethoxylated quaternary) and 760.0g deionized water be heated to 50 degrees Celsius of high speed shear and stir and obtain the pre-emulsion that particle diameter is less than 100nm, then logical nitrogen deoxygenation adds azo-bis-isobutyrate hydrochloride and the 50.0g vinylidene chloride of 0.2g after 30 minutes, be warming up to 55-65 degree Celsius, after insulation reaction 10 hours, filter discharging.
Embodiment 7
Floride-free water-proofing composition synthetic: by the compd A in Methacrylamide, the 200.0g embodiment 3 of 150.0g acrylic acid mountain Yu base ester, 10g, 40.0gTergitol15-s-15 (DOW Chemical product), 3.0gEthoquadHT25(ethoxylated quaternary) and 760.0g deionized water be heated to 50 degrees Celsius of high speed shear stirrings and obtain the pre-emulsion that particle diameter is less than 100nm, then logical nitrogen deoxygenation adds azo-bis-isobutyrate hydrochloride and the 45.0g vinylidene chloride of 0.2g after 30 minutes, be warming up to 55-65 degree Celsius, after insulation reaction 10 hours, filter discharging.
Embodiment 8
Synthesizing of floride-free water-proofing composition: the compd A in Methacrylamide, the 120.0g embodiment 4 of 150.0g acrylic acid mountain Yu base ester, 2g, 30.0gTergitol15-s-15 (DOW Chemical product), 3.0g hexadecyltrimethylammonium chloride and 760.0g deionized water are heated to 50 degrees Celsius of high speed shear stirrings and obtain the pre-emulsion that particle diameter is less than 100nm, then logical nitrogen deoxygenation adds azo-bis-isobutyrate hydrochloride and the 35.0g vinylidene chloride of 0.2g after 30 minutes, be warming up to 55-65 degree Celsius, after insulation reaction 10 hours, filter discharging.
Application on fabric
By floride-free water-proofing composition synthetic in embodiment 5 to 8, be diluted to 100g/l, then pure terylen and textile plain weaving machine are weaved cotton cloth, in dilution, carry out traditional one and soak a roll process, pick-up is 70-80%, then under 100 degrees Celsius, after predrying 1 minute, bake after 2 minutes under 150 degrees Celsius, cool to room temperature is tested its waterproof effect.
For verify through of the present invention process without fluoro water proofing agent after the waterproof effect of textile, can adopt GB GB4745-1997 to investigate waterproof effect, be method brief introduction below:
Intercept the sample of 18X18cm, compress with clamper, and be installed on to become with level on the firm banking with 45° angle, by the distilled water of 250mL (20 ± 2 ° of C) or deionized water rapidly and reposefully in hopper, by with the shower nozzle of sample centre distance in 25 30s, on average and continuously spray towards sample center. Spray completely, rapidly clamper is taken away, make the sample level of facing down into, pat lightly twice, observe sample wetness degree, then by text description and contrast with picture and evaluate its grade. Table 1 is the result after test.
Table 1
From the result of table 1, can find out, floride-free water-proofing composition disclosed by the invention all has good waterproof effect on textile or pure terylen; In addition washing fastness is also relatively good, even after the family washing of experience 10 times, it is still relatively good that waterproof effect keeps.
Claims (10)
1. a water-fastness floride-free water-proofing composition, is characterized in that, its component is as follows, by weight percentage: the compd A of 25-60%; The acrylate polymer of 15-40%; The emulsifying agent of 3-40%; Other is water.
2. water-fastness floride-free water-proofing composition as claimed in claim 1, is characterized in that, described chemical combination A is synthetic by the fatty alcohol of isocyanates and long-chain or fatty amine.
3. water-fastness floride-free water-proofing composition as claimed in claim 2, is characterized in that, the fatty alcohol of described long-chain is direct-connected or the aliphatic alcohol that contains side chain, represents with structural formula below:
Wherein, R1, R2, R3 can be with representing that formula X-Y-Z or Z represent:
X is with representing Shi – (CH2) t-represents, t=0-30;
Y with represent Shi-O-C (O)-or-O-C (O)-NH-represents;
Z is with representing Shi – (CH2)m-HRepresent m=0-30;
Wherein, R4Can be with representing Shi – (CH2)p-(OCH2CH2)q-(OCH2CH(CH3))r-OH represents, p, q and r=0-30.
4. water-fastness floride-free water-proofing composition as claimed in claim 2, is characterized in that, the fatty amine of described long-chain is direct-connected or the aliphatic amine that contains side chain, represents with structural formula below:
Wherein, n=0-2; Q is with representing Shi-(CH2) y-represents, y=1-4; B4Be H or
–(CH2)f-H，f=0-30；B1，B2，B3With representing that formula V-W-U or U represent:
V is with representing Shi – (CH2)d-represent d=0-30;
W with represent Shi-O-C (O)-or-O-C (O)-NH-represents;
U is with representing Shi – (CH2)e-H represents, e=0-30.
5. water-fastness floride-free water-proofing composition as claimed in claim 2, is characterized in that, described isocyanates be end-blocking or end-blocking not, degree of functionality is between 1.8-5.
6. water-fastness floride-free water-proofing composition as claimed in claim 2, is characterized in that, the mol ratio of the fatty alcohol of described long-chain or fatty amine and isocyanates is that 1:10 is to 1:1.3.
7. water-fastness floride-free water-proofing composition as claimed in claim 1, it is characterized in that, described acrylate polymer is the copolymer of construction unit composition below: by weight percentage, the acrylate or the methacrylate that contain 10 to 24 carbon atoms of 25-60%, or the mixture of acrylate and methacrylate; 10% to 40% vinylidene chloride; 10% to 40% the acrylate that contains functional group or methacrylate, or the mixture of acrylate and methacrylate; 0.0001% to 0.1% initator.
8. water-fastness floride-free water-proofing composition as claimed in claim 7, is characterized in that, described in contain 10 to 24 carbon atoms acrylate or methacrylate be side chain, or be also straight chain or ring-type.
9. water-fastness floride-free water-proofing composition as claimed in claim 7, is characterized in that, described functional group refers to and contains hydroxyl, or epoxy radicals, or amide groups, or carboxyl, or alkoxyl, or the NCO of sealing.
10. water-fastness floride-free water-proofing composition as claimed in claim 7, is characterized in that, described initator refers to the initiator system of one or several or redox class in water miscible a kind of persulfuric acid salt or azo.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106087420A (en) * | 2016-06-07 | 2016-11-09 | 苏州联胜化学有限公司 | A kind of without fluoro water proofing agent and preparation method thereof |
| CN109715879A (en) * | 2016-09-23 | 2019-05-03 | 亨茨曼纺织货品（德国）有限责任公司 | The not fluorine-containing water-borne dispersions arranged for textile fabric |
| CN109988264A (en) * | 2017-12-29 | 2019-07-09 | 乳源东阳光氟有限公司 | A kind of no fluoro water proofing agent and its preparation method and application |
| CN114933681A (en) * | 2022-05-16 | 2022-08-23 | 杭州美高华颐化工有限公司 | Isocyanate modified polyacrylate fluorine-free waterproof agent and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106087420A (en) * | 2016-06-07 | 2016-11-09 | 苏州联胜化学有限公司 | A kind of without fluoro water proofing agent and preparation method thereof |
| CN109715879A (en) * | 2016-09-23 | 2019-05-03 | 亨茨曼纺织货品（德国）有限责任公司 | The not fluorine-containing water-borne dispersions arranged for textile fabric |
| CN109715879B (en) * | 2016-09-23 | 2022-07-05 | 亨茨曼纺织货品（德国）有限责任公司 | Fluorine-free aqueous dispersions for textile finishing |
| CN109988264A (en) * | 2017-12-29 | 2019-07-09 | 乳源东阳光氟有限公司 | A kind of no fluoro water proofing agent and its preparation method and application |
| CN109988264B (en) * | 2017-12-29 | 2022-03-04 | 乳源东阳光氟有限公司 | Fluorine-free waterproof agent and preparation method and application thereof |
| CN114933681A (en) * | 2022-05-16 | 2022-08-23 | 杭州美高华颐化工有限公司 | Isocyanate modified polyacrylate fluorine-free waterproof agent and preparation method thereof |
| CN114933681B (en) * | 2022-05-16 | 2023-11-21 | 杭州美高华颐化工有限公司 | Isocyanate modified polyacrylate fluorine-free waterproof agent and preparation method thereof |
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Application publication date: 20160525 |