CN107653681B - High-effective water-proof oil-proofing agent and preparation method comprising telechelic polymer - Google Patents
High-effective water-proof oil-proofing agent and preparation method comprising telechelic polymer Download PDFInfo
- Publication number
- CN107653681B CN107653681B CN201710999753.1A CN201710999753A CN107653681B CN 107653681 B CN107653681 B CN 107653681B CN 201710999753 A CN201710999753 A CN 201710999753A CN 107653681 B CN107653681 B CN 107653681B
- Authority
- CN
- China
- Prior art keywords
- telechelic polymer
- methyl
- water
- monomer
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- 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
-
- 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
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
-
- 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
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
- D06M2200/11—Oleophobic properties
-
- 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
-
- 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
- D06M2200/50—Modified hand or grip properties; Softening compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention discloses a kind of high-effective water-proof oil-proofing agent comprising telechelic polymer, the water and oil repellent agent includes following components by mass percentage: fluoropolymer 20-35%, surfactant 2-8%, auxiliary agent 2-10% and water.Water and oil repellent agent provided by the invention has good waterproof oil-proof result.Water and oil repellent agent provided by the invention compared with the prior art, has better waterproof oil-proof result and excellent handle, washing resistance performance is more preferably using special material.
Description
Technical field
The present invention relates to textile auxiliary field, specifically a kind of water and oil repellent agent and its system comprising telechelic polymer
Preparation Method.
Background technique
Water and oil repellent agent can assign the performance of textile surface hydrophobic oleophobic.Most commonly used in the market is fluorine-containing waterproof
Oil-proofing agent.Current water and oil repellent agent haves the shortcomings that feel is bad and washability is poor mostly, and the efficiency of waterproof oil-proof finishing is also
It is to be improved.These disadvantages, which are traced sth. to its source, is the Molecular Design defect of waterproofing agent.
(Kubo member Shen Fluorine-Contained Oil-Water-Proofing (I) --- mechanism [J] about waterproof and oilproof performance prints for Kubo member Shen
Dye, 1995,21 (12): 37-41) list the molecular structure of conventional water and oil repellent agent: by functional monomer in the process of arrangement
In reaction realize and self-crosslinking or reacted with fabric, crosslinking agent, to improve persistence.Functional monomer is in waterproofing agent main chain
It is upper formed band can reactive group short-side chain, the reaction of reactive group forms very strong effect of contraction to main chain, and formation is hardened
Feel；Simultaneously as the steric hindrance of main chain, many reactive group self-crosslinkings do not form stronger combination with fabric, it is resistance to
Long property is promoted unobvious.
Summary of the invention
The present invention is intended to provide a kind of high-effective water-proof oil-proofing agent and its manufacturing method comprising telechelic polymer, the waterproof is anti-
Finish is more able to maintain the feel of fabric itself, has better waterproof oil-proof result and persistence.
To achieve the above object, present invention firstly provides a kind of water and oil repellent agents, which is characterized in that each component and quality hundred
Divide ratio as follows:
Fluoropolymer 20-35%, surfactant 2-8%, auxiliary agent 2-10%, surplus are water；
The fluoropolymer is passed through by fluorochemical monomer A, fluorochemical monomer B, non-fluorine monomer, function monomer and telechelic polymer
Free radical polymerization forms, and the fluorochemical monomer A, fluorochemical monomer B, non-fluorine monomer, function monomer and telechelic polymer account for fluorine-containing poly-
Close the mass percent of object are as follows: fluorochemical monomer A accounts for 19-55%, and fluorochemical monomer B accounts for 1-5%, non-fluorine monomer 20-70%, function
Monomer 5-20% and telechelic polymer 5-10%；
The general formula of the fluorochemical monomer A is CmF2m+1YCnH2nOCOCR=CH2, wherein Y be chemical single bond or-NH- ,-
NR1-、-NH-SO2-、-NR1-SO2One or more, R1It is C1—C4One kind of alkyl；R is H, Cl, F or CH3；M is 4,5,6
In any integer, any integer in n 1,2,3,4；It can be the mixing for meeting a kind of substance or many kinds of substance of general formula
Object.
The fluorochemical monomer B by 2mol perfluoro hexyl ethyl alcohol, 1mol hexamethylene diisocyanate (HDI) tripolymer and
1mol hy-droxybutyl reacts to obtain；
The non-fluorine monomer has hydrocarbon hydrophobic grouping and double bond, and hydrocarbon hydrophobic grouping can be straight chain, branch or (more)
One or more mixing of cricoid hydrophobic alkyl.
The function monomer has a double bond and functional group, and the function monomer is a kind of substance or many kinds of substance
Mixture；
The telechelic polymer is selected from one end and has double bond, and other end has thermal deblocking type blocked isocyanate group
One or more kinds of telechelic polymer mixing；
The surfactant is selected from nonionic and cationic surface active agent；
The auxiliary agent includes that pH adjusts auxiliary agent, secondary solvent；
The free radical is to be thermally decomposed to generate by initiator；
The hydrocarbon hydrophobic grouping can be straight chain, the branched alkyl of carbon number >=8, and (alkyl substitution) phenyl, (alkyl takes
Generation) cyclohexyl, one or more mixing of isobornyl；
The functional group of the function monomer be selected from containing epoxy group or hydroxyl or amino or carboxyl or ketone carbonyl or
Tri-alkoxy silicon substrate or one and more than one carbon-to-carbon double bond have polyethylene oxide segments or tertiary amine group or quaternary ammonium group
It rolls into a ball or with the one or more of chlorine element etc.；
The function monomer is selected from glycidyl methacrylate, acrylamide, vinyltrimethoxysilane, double third
Ketone acrylamide cooperate adipic dihydrazide system, ethylene glycol dimethacrylate, trimethylolpropane tris (methyl) acrylate,
Divinylbenzene, (methyl) dimethylaminoethyl acrylate, (methoxyl group) polyethylene glycol (methyl) acrylate, (methyl) propylene
Acyloxyethyl trimethyl ammonium chloride, vinyl chloride, vinylidene chloride, 3- chlorine-2-hydroxyl-propyl methacrylate, (methyl) third
One or more of olefin(e) acid hydroxyl ethyl ester；
The telechelic polymer is by (methyl) crylic acid hydroxy ester, polyisocyanates, low molecular weight diol and end-capping reagent
Reaction obtains, one terminal double bond, and other end is thermal deblocking type blocked isocyanate.
(methyl) crylic acid hydroxy ester of the synthesis telechelic polymer is selected from (methyl) hydroxy-ethyl acrylate, (methyl) third
Olefin(e) acid hydroxy butyl ester and the own ester of (methyl) acrylic acid hydroxyl are one or more kinds of；The polyisocyanates is selected from isophorone diisocyanate
Ester (IPDI), toluene di-isocyanate(TDI) (TDI), hexamethylene diisocyanate (HDI), methyl diphenylene diisocyanate
(MDI), HDI trimer, TDI tripolymer, MDI tripolymer it is one or more；Low molecular weight diol is selected from molecular weight 100-
1000 polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol, polyhexamethylene adipate glycol, polybutyleneadipate
One of esterdiol, polyneopentyl glycol adipate glycol, polycaprolactone glycol, straight chained alkyl glycol are a variety of；The envelope
Agent is held to be selected from one of 3,5- dimethyl pyrazole, diacetylmonoxime, phenol, diethyl malonate or a variety of；
It includes acid or alkali or amino acid that the pH, which adjusts auxiliary agent, and water and oil repellent agent pH value is between 4~7；
The secondary solvent is selected from one or two kinds of mixtures of dipropylene glycol ethyl ether, tripropylene glycol ether；
The initiator is selected from one of persulfate, oil-soluble azo-initiator or water-soluble azo class initiator
Or it is a variety of；
The initiator is selected from one of ammonium persulfate, azodiisobutyronitrile, azo-bis-isobutyrate hydrochloride or a variety of；
A kind of preparation method of water and oil repellent agent, comprising the following steps:
(1) each component is uniformly mixed and is emulsified, obtain pre-emulsion, do not include initiator, water-soluble monomer in pre-emulsion
It is lower than the substance of emulsifying temperature with boiling point；
(2) pre-emulsion that step (1) obtains first is added in water-soluble monomer, be uniformly mixed.Then initiator is added anti-
It answers, boiling point is added at one time or is gradually added lower than the substance of emulsifying temperature, and system temperature is down to room after reaction
Temperature obtains target product after filtering.
It wherein, can also include the molecular weight regulator of system mass percent 0~0.3% in the polymerization system.Institute
Stating molecular weight regulator can be alkyl hydrosulfide, α-methyl styrene linear dimerization body, mercaptopropionic acid etc..Preferable selection is
The alkyl hydrosulfide of the straight chain of 12 or more carbon number.
The beneficial effects of the present invention are:
Water and oil repellent agent is synthesized using special fluorochemical monomer B and telechelic polymer, embody the fabric after arranging more can
The feel of itself, waterproof and oilproof performance and washing fastness are more preferable.
Specific embodiment
In order to verify through water and oil repellent agent of the present invention processing after textile waterproof effect, can by standard method into
Row is investigated, to compare.The standard method is that waterproof effect is investigated using national standard GB 4745-2012, and grease proofing effect is used
AATCC-TEST Method l18-2002 is investigated, and here is method brief introduction.
National standard " GB 4745-2012 " test method.
The sample for intercepting 18 × 18cm, is compressed with clamper, and is installed on horizontal on the firm banking with 45° angle,
With the distilled water or deionized water of 250mL (20 ± 2 DEG C) rapidly and smoothly in hopper, by being located at sample overcentre
Spray head in 25~30s, it is average towards sample center and continuously spray.Spray finishes, and rapidly takes away clamper, makes
The sample level of facing down into is lightly patted, is then rotated, and is made the sample level of facing up into, is lightly patted one
Under, sample wetness degree is observed, is compareed with verbal description and with picture and evaluates its grade.Take 2 average values.
Rating scale text are as follows:
0 grade --- entire specimen surface complete wetting.
L grades --- by leaching surface complete wetting.
L-2 grades --- beyond soaking at spray point, wetting areas exceeds by leaching surface half specimen surface.
2 grades --- specimen surface at spray point beyond soaking, and wetting areas is about by leaching surface half.
2-3 grades --- beyond soaking at spray point, wetting areas is less than by leaching surface half specimen surface.
3 grades --- it is soaked at specimen surface spray point.
3-4 grades --- specimen surface, which is equal to or less than at the spray point of half, to be soaked.
4 grades --- specimen surface has to be soaked at fragmentary spray point.
4-5 grades --- specimen surface does not soak, and has a small amount of droplet.
5 grades --- specimen surface does not have droplet or wetting.
AATCC-TEST Method l18-2002 method: the experimental liquid of lowest number is used, first with 0.05mL liquid
Body is carefully dripped on sample, if occurred in 30 seconds without infiltration and wetting phenomena, and then uses the experiment liquid of higher number
Body is dripped on sample.Experiment is carried out continuously, until experimental liquid in 30 seconds the fountain solution side of dripping or around until sample.Sample
Refuse oily grade cannot soak the experimental liquid of the highest number of sample in 30 seconds and indicate, rating such as following table.
1 grease proofness testing standard liquid of table
| Grease proofing series | Component | Surface tension (mN/m, 25 DEG C) |
| 1 | White Mineral Oil | 31.2 |
| 2 | 35 parts of 65 parts+hexadecane of White Mineral Oil | 28.7 |
| 3 | Hexadecane | 27.1 |
| 4 | N-tetradecane | 26.1 |
| 5 | N-dodecane | 25.1 |
| 6 | N-decane | 23.5 |
| 7 | Normal octane | 21.3 |
| 8 | Normal heptane | 19.8 |
The effect of sample after washing is also investigated, washing conditions are standard synthetic detergent 1g/L, washing machine bath raio 1:
30 washings, rinse, dehydration, the drying of 100 DEG C × 3min forming machine.
Telechelic polymer A
Take the own ester of 1mol acrylic acid hydroxyl and 1mol isophorone diisocyanate (IPDI) fully reacting；Add 1mol's
1,5 hexylene glycol fully reactings；Then the IPDI tripolymer fully reacting of 1mol is added；It is eventually adding the 3,5- dimethyl pyrazole of 2mol
Azoles is reacted to terminal, obtains telechelic polymer A.
Telechelic polymer B
Take 1mol hy-droxybutyl and 1mol toluene di-isocyanate(TDI) (TDI) fully reacting；Add 1mol molecular weight
500 polycaprolactone glycol fully reacting；Then the TDI tripolymer fully reacting of 1mol is added；It is eventually adding the butanone of 2mol
Oxime is reacted to terminal, obtains telechelic polymer B.
Telechelic polymer C
Take 1mol hydroxy-ethyl acrylate and 1mol isophorone diisocyanate (IPDI) fully reacting；Add 1mol points
The polyhexamethylene adipate glycol fully reacting of son amount 1000；Then the HDI trimer fully reacting of 1mol is added；Finally plus
3, the 5- dimethyl pyrazole for entering 2mol is reacted to terminal, obtains telechelic polymer C.
Embodiment 1
11 grams of methacrylic acid perfluoro hexyl ethyl esters are taken, 1 gram of fluorochemical monomer B is (by 2mol perfluoro hexyl ethyl alcohol, 1mol
Hexamethylene diisocyanate (HDI) tripolymer and 1mol hy-droxybutyl react to obtain), 10.4 grams of acrylic acid behenyl bases
Ester, 2 grams of styrene, 2 grams of telechelic polymer B, 5.7 grams of dipropylene glycol ethyl ethers, 5 grams of Ethoqual C/25 (ethoxylated quaternary ammoniums
Salt), 0.3 gram of acetic acid, 58.8 grams of water heat up 55 degree, and high speed emulsification 60 minutes obtains pre-emulsion；Logical nitrogen 30 minutes again, simultaneously
Controlled at 62 DEG C.It is added 0.2 gram of azo-bis-isobutyrate hydrochloride, 3.6 grams of vinyl chloride, insulation reaction 8 hours.Finally by body
It is that temperature is down to room temperature, through 300 mesh filter-cloth filterings to get water and oil repellent agent.
Other embodiments
Each component and 1 different from of embodiment in other embodiments, preparation process is same as Example 1, hereinafter, with subordinate list
Form lists the component of each embodiment.
Comparative example 1
There is no special material in water and oil repellent agent.
Take 12 grams of methacrylic acid perfluoro hexyl ethyl esters, 12.4 grams of acrylic acid behenyl base esters, 2 grams of styrene, 5.7 gram two
Propylene-glycol ethyl ether, 5 grams of Ethoqual C/25 (ethoxylated quaternary), 0.3 gram of acetic acid, 58.8 grams of water heat up 55 degree, high speed
Emulsification 60 minutes, obtains pre-emulsion；Lead to again nitrogen 30 minutes, while controlled at 62 DEG C.0.2 gram of two NSC 18620 of azo is added
Hydrochloride, 3.6 grams of vinyl chloride, insulation reaction 8 hours.System temperature is finally down to room temperature, through 300 mesh filter-cloth filterings to get
Water and oil repellent agent.
Comparative example 2
Water and oil repellent agent is commercial goods.
It is 5% that embodiment 1-5 and the water and oil repellent agent of comparative example 1-2, which are diluted to solid content with tap water, is taken
One immersing and rolling of tatting cotton fabric, 100 DEG C of drying, 180 DEG C are heat-treated 30 seconds, measure waterproof effect after being cooled to room temperature.
| Number | Waterproof | It is grease proofing | Waterproof after washing 10 times | It is grease proofing after washing 10 times |
| Embodiment 1 | 5 | 5-6 | 4-5 | 5 |
| Embodiment 2 | 5 | 5-6 | 5 | 4-5 |
| Embodiment 3 | 5 | 6 | 5 | 5-6 |
| Embodiment 4 | 5 | 5-6 | 4-5 | 4-5 |
| Embodiment 5 | 5 | 6 | 5 | 5 |
| Comparative example 1 | 4-5 | 4-5 | 4 | 4 |
| Comparative example 2 | 4-5 | 4-5 | 3 | 3-4 |
In addition, cloth specimen of the cloth-like hand arranged through embodiment 1-5 closer to before arranging, and after comparative example arranges
Cloth specimen obviously has stiff feel.
The present invention also provides a kind of application of above-mentioned water and oil repellent agent on the textile.Applying step includes: first will be above-mentioned
Water and oil repellent agent is diluted to 0.1-10% mass fraction, is then applied on the cotton fabric through low-temperature dyeing and finishing processing；Then it removes
Extra liquid, is finally dried.The methods of coating, spraying, roller coating, pad dyeing, dipping and these sides can be passed through
Water and oil repellent agent is applied on the cotton fabric through low-temperature dyeing and finishing processing by the combination of method.It is detected, is attached to and adds through low-temperature dyeing and finishing
The mass ratio that water and oil repellent agent ingredient on the cotton fabric of work accounts for the cotton fabric through low-temperature dyeing and finishing processing is 0.01% -10%.
In the drying process, drying condition according to the difference for the cotton fabric type processed through low-temperature dyeing and finishing and difference, while should
Guarantee sufficiently to be reacted in water and oil repellent agent by function monomer bring functional group, to reach optimal waterproof oil-proof result and resistance to
Long property, it usually needs 0.1-90 minutes dry at 100 DEG C-200 DEG C.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several changes, improvements and modifications, these change, improve and moisten
Decorations also should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of high-effective water-proof oil-proofing agent comprising telechelic polymer, which is characterized in that each component and mass percent are as follows:
Fluoropolymer 20-35%, surfactant 2-8%, auxiliary agent 2-10%, surplus are water；
The fluoropolymer passes through freedom by fluorochemical monomer A, fluorochemical monomer B, non-fluorine monomer, function monomer and telechelic polymer
Base is polymerized, and the fluorochemical monomer A, fluorochemical monomer B, non-fluorine monomer, function monomer and telechelic polymer account for fluoropolymer
Mass percent are as follows: fluorochemical monomer A accounts for 19-55%, and fluorochemical monomer B accounts for 1-5%, non-fluorine monomer 20-70%, function monomer
5-20% and telechelic polymer 5-10%；
The general formula of the fluorochemical monomer A is CmF2m+1YCnH2nOCOCR=CH2, wherein Y is chemical single bond or-NH- ,-NR1-、-
NH-SO2-、-NR1-SO2One or more, R1It is C1—C4One kind of alkyl；R is H, Cl, F or CH3；M is in 4,5,6
Any integer, any integer in n 1,2,3,4；It can be the mixture of a kind of substance or many kinds of substance that meet general formula；
The fluorochemical monomer B by 2mol perfluoro hexyl ethyl alcohol, 1mol hexamethylene diisocyanate (HDI) tripolymer and
1mol hy-droxybutyl reacts to obtain；
The non-fluorine monomer has hydrocarbon hydrophobic grouping and double bond, and hydrocarbon hydrophobic grouping can be straight chain, branch or cricoid thin
One or more mixing of water alkyl；
The function monomer has a double bond and functional group, and the function monomer is the mixed of a kind of substance or many kinds of substance
Close object；
The telechelic polymer is by (methyl) crylic acid hydroxy ester, polyisocyanates, low molecular weight diol and blocking agent reaction
It obtains, one terminal double bond, other end is thermal deblocking type blocked isocyanate；
The surfactant is selected from nonionic and cationic surface active agent；
The auxiliary agent includes that pH adjusts auxiliary agent, secondary solvent；
The free radical is to be thermally decomposed to generate by initiator.
2. the high-effective water-proof oil-proofing agent according to claim 1 comprising telechelic polymer, which is characterized in that described hydrocarbon thin
Water base group can be carbon number >=8 straight chain, branched alkyl, (alkyl substitution) phenyl, (alkyl substitution) cyclohexyl, isobornyl
One or more mixing.
3. the high-effective water-proof oil-proofing agent according to claim 1 comprising telechelic polymer, which is characterized in that the function list
The functional group of body is selected from containing epoxy group or hydroxyl or amino or carboxyl or ketone carbonyl or tri-alkoxy silicon substrate or one
A above carbon-to-carbon double bond or one kind with polyethylene oxide segments or tertiary amine group or quaternary ammonium group or with chlorine element etc. or
It is a variety of.
4. the high-effective water-proof oil-proofing agent according to claim 3 comprising telechelic polymer, which is characterized in that the function list
Body is selected from glycidyl methacrylate, acrylamide, vinyltrimethoxysilane, Diacetone Acrylamide cooperate oneself two
Hydrazides system, ethylene glycol dimethacrylate, trimethylolpropane tris (methyl) acrylate, divinylbenzene, (methyl)
Dimethylaminoethyl acrylate, (methoxyl group) polyethylene glycol (methyl) acrylate, (methyl) acrylyl oxy-ethyl-trimethyl chlorine
Change ammonium, vinyl chloride, vinylidene chloride, 3- chlorine-2-hydroxyl-propyl methacrylate, one in (methyl) hydroxy-ethyl acrylate
Kind is several.
5. the high-effective water-proof oil-proofing agent according to claim 1 comprising telechelic polymer, which is characterized in that (methyl)
It is a kind of that crylic acid hydroxy ester is selected from (methyl) hydroxy-ethyl acrylate, (methyl) hy-droxybutyl and the own ester of (methyl) acrylic acid hydroxyl
Or it is a variety of；The polyisocyanates is selected from isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI), six Asias
Methyl diisocyanate (HDI), methyl diphenylene diisocyanate (MDI), HDI trimer, TDI tripolymer, MDI tripolymer
It is one or more；Low molecular weight diol is selected from polyethylene glycol, the polypropylene glycol, polytetrahydrofuran ether two of molecular weight 100-1000
Alcohol, polyhexamethylene adipate glycol, polybutylene glyool adipate, polyneopentyl glycol adipate glycol, polycaprolactone
One of glycol, straight chained alkyl glycol are a variety of；The end-capping reagent is selected from 3,5- dimethyl pyrazole, diacetylmonoxime, phenol, the third two
One of diethyl phthalate is a variety of.
6. the high-effective water-proof oil-proofing agent according to claim 1 comprising telechelic polymer, which is characterized in that the pH is adjusted
Auxiliary agent includes acid or alkali or amino acid, and water and oil repellent agent pH value is between 4~7；The secondary solvent is selected from two
One or two kinds of mixtures of propylene-glycol ethyl ether, tripropylene glycol ether.
7. the high-effective water-proof oil-proofing agent according to claim 1 comprising telechelic polymer, which is characterized in that the initiator
Selected from one of persulfate, oil-soluble azo-initiator or water-soluble azo class initiator or a variety of.
8. the high-effective water-proof oil-proofing agent according to claim 7 comprising telechelic polymer, which is characterized in that the initiator
Selected from one of ammonium persulfate, azodiisobutyronitrile, azo-bis-isobutyrate hydrochloride or a variety of.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910701158.4A CN110485160B (en) | 2017-10-24 | 2017-10-24 | Preparation method of efficient water-proof and oil-proof agent containing telechelic polymer |
| CN201710999753.1A CN107653681B (en) | 2017-10-24 | 2017-10-24 | High-effective water-proof oil-proofing agent and preparation method comprising telechelic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710999753.1A CN107653681B (en) | 2017-10-24 | 2017-10-24 | High-effective water-proof oil-proofing agent and preparation method comprising telechelic polymer |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910701158.4A Division CN110485160B (en) | 2017-10-24 | 2017-10-24 | Preparation method of efficient water-proof and oil-proof agent containing telechelic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107653681A CN107653681A (en) | 2018-02-02 |
| CN107653681B true CN107653681B (en) | 2019-10-25 |
Family
ID=61119453
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710999753.1A Active CN107653681B (en) | 2017-10-24 | 2017-10-24 | High-effective water-proof oil-proofing agent and preparation method comprising telechelic polymer |
| CN201910701158.4A Active CN110485160B (en) | 2017-10-24 | 2017-10-24 | Preparation method of efficient water-proof and oil-proof agent containing telechelic polymer |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910701158.4A Active CN110485160B (en) | 2017-10-24 | 2017-10-24 | Preparation method of efficient water-proof and oil-proof agent containing telechelic polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN107653681B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110670359B (en) * | 2019-10-10 | 2022-02-11 | 广东中联邦精细化工有限公司 | Low-temperature type waterproof and oil-proof agent and preparation method thereof |
| CN111877017A (en) * | 2020-07-10 | 2020-11-03 | 温州厚德服饰有限公司 | Waterproof cotton-padded clothes |
| CN112538760A (en) * | 2020-11-24 | 2021-03-23 | 京准化工技术(上海)有限公司 | Six-carbon fluorine-series high-washing-resistance waterproof and oil-proof agent and preparation method thereof |
| CN113089325B (en) * | 2021-06-08 | 2022-06-10 | 广东德美精细化工集团股份有限公司 | Durable short-chain fluorine-containing water and oil repellent agent and preparation method thereof |
| CN114687210A (en) * | 2021-12-22 | 2022-07-01 | 浙江科峰新材料有限公司 | Environment-friendly washable waterproof and oil-proof agent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2120813A1 (en) * | 1971-03-08 | 1972-09-28 | Blöchl, Walter, 7500 Karlsruhe | Oleophobic impregnation of fibrous-porous substrates. Eliminated from: 2110912 |
| JPH01131135A (en) * | 1987-11-16 | 1989-05-24 | Asahi Chem Ind Co Ltd | Perfluropolyether diacrylate |
| CN101578308A (en) * | 2007-01-17 | 2009-11-11 | 旭硝子株式会社 | Oil-repellent copolymer, method for producing the same and oil-repellent processing liquid |
| CN102002129A (en) * | 2010-10-25 | 2011-04-06 | 江苏梅兰化工有限公司 | Method for preparing fluorine-containing acrylate copolymer textile finishing agent |
| CN103266482A (en) * | 2013-03-23 | 2013-08-28 | 广东德美精细化工股份有限公司 | Wax-containing water-and-oil repellent agent and preparation method, textile |
| CN106758232A (en) * | 2016-11-29 | 2017-05-31 | 广东德美高新材料有限公司 | Bafta special-purpose water-proof oil-proofing agent, preparation method and its bafta processed through full low-temperature dyeing and finishing |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6437077B1 (en) * | 1998-04-09 | 2002-08-20 | Clariant Finance (Bvi) Limited | Blocked oligomeric isocyanates, their production and use |
| US6479605B1 (en) * | 2001-05-15 | 2002-11-12 | E. I. Du Pont De Nemours And Company | High-durability, low-yellowing repellent for textiles |
| US6979711B2 (en) * | 2003-11-18 | 2005-12-27 | E. I. Du Pont De Nemours And Company | Fluorine efficient finishes for textiles |
| JP4752197B2 (en) * | 2004-06-04 | 2011-08-17 | ユニマテック株式会社 | Manufacturing method of water and oil repellent |
| JP5353697B2 (en) * | 2007-06-12 | 2013-11-27 | 旭硝子株式会社 | Water / oil repellent composition, method for producing the same, and article |
| US9677220B2 (en) * | 2009-11-20 | 2017-06-13 | Daikin Industries, Ltd. | Fluoropolymers and treatment agent |
| KR101819978B1 (en) * | 2013-06-25 | 2018-01-19 | 유니마테크 가부시키가이샤 | Aqueous dispersion of fluorinated copolymer |
-
2017
- 2017-10-24 CN CN201710999753.1A patent/CN107653681B/en active Active
- 2017-10-24 CN CN201910701158.4A patent/CN110485160B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2120813A1 (en) * | 1971-03-08 | 1972-09-28 | Blöchl, Walter, 7500 Karlsruhe | Oleophobic impregnation of fibrous-porous substrates. Eliminated from: 2110912 |
| JPH01131135A (en) * | 1987-11-16 | 1989-05-24 | Asahi Chem Ind Co Ltd | Perfluropolyether diacrylate |
| CN101578308A (en) * | 2007-01-17 | 2009-11-11 | 旭硝子株式会社 | Oil-repellent copolymer, method for producing the same and oil-repellent processing liquid |
| CN102002129A (en) * | 2010-10-25 | 2011-04-06 | 江苏梅兰化工有限公司 | Method for preparing fluorine-containing acrylate copolymer textile finishing agent |
| CN103266482A (en) * | 2013-03-23 | 2013-08-28 | 广东德美精细化工股份有限公司 | Wax-containing water-and-oil repellent agent and preparation method, textile |
| CN106758232A (en) * | 2016-11-29 | 2017-05-31 | 广东德美高新材料有限公司 | Bafta special-purpose water-proof oil-proofing agent, preparation method and its bafta processed through full low-temperature dyeing and finishing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110485160A (en) | 2019-11-22 |
| CN110485160B (en) | 2022-02-15 |
| CN107653681A (en) | 2018-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107653681B (en) | High-effective water-proof oil-proofing agent and preparation method comprising telechelic polymer | |
| CN111386327B (en) | Water repellent composition and process for producing water repellent fiber product | |
| CN109790679B (en) | Hydrophobic agent composition and method for producing hydrophobic fiber product | |
| CN106758232B (en) | Cotton fabric special-purpose water-proof oil-proofing agent, preparation method and its cotton fabric processed through full low-temperature dyeing and finishing | |
| CN106637976B (en) | The cotton fabric high-efficient, no-freon waterproofing agent processed through low-temperature dyeing and finishing | |
| US7652112B2 (en) | Polymeric extenders for surface effects | |
| JP6435320B2 (en) | Urethane polymer extenders for compositions that modify the surface properties of substrates | |
| US5817249A (en) | Carbodiimide compound and water repellent compositions | |
| DE69705399T2 (en) | A GOOD PERFORMANCE OF BOTH AIR DRYING LUBRICATING FLUOROCHEMICAL POLYURETHANES | |
| EP2841480B1 (en) | Fluorochemical compounds, compositions, articles, and methods | |
| WO2017199726A1 (en) | Water repellent and production process therefor | |
| CN103628317B (en) | A kind of composition of waterproofing and oil-proof agent and processing method, textiles | |
| CN107435245B (en) | Method for producing water-repellent fiber product | |
| EP3075813A1 (en) | Water- and oil-repellent composition, article and process for producing article | |
| KR20180034443A (en) | Non-fluorine polymer, water repellent composition, water repellent fiber product, and method for producing water repellent fiber product | |
| CA2319735A1 (en) | Stabilization of fluorochemical copolymer emulsions | |
| CN110452361B (en) | Synthetic method of polyurethane acrylic acid modified organic silicon fluoride-free waterproof agent and waterproof agent | |
| US10822500B2 (en) | Preparations as hydrophobing agents | |
| CN110485159A (en) | The preparation method of high-efficient, no-freon waterproofing agent comprising telechelic polymer | |
| JP2023085382A (en) | Water-repellant composition, water-repellent fiber product, and method for manufacturing water-repellent fiber product | |
| EP3778824A1 (en) | Oil-repellent and water-repellent agent composition, article, and method for producing article | |
| CN110267998B (en) | Polymers for hydrophobic and oleophobic textile finishing | |
| CN106758252A (en) | Easy care type water and oil repellent agent and preparation method thereof, textile | |
| CN112673128A (en) | Water repellent composition for fibers, water repellent fiber product, and method for producing water repellent fiber product | |
| CN113227486A (en) | Water repellent composition and method for producing water repellent fiber product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |