CN113461875B - Silicon-containing treating agent and preparation and application thereof - Google Patents

Silicon-containing treating agent and preparation and application thereof Download PDF

Info

Publication number
CN113461875B
CN113461875B CN202110850269.9A CN202110850269A CN113461875B CN 113461875 B CN113461875 B CN 113461875B CN 202110850269 A CN202110850269 A CN 202110850269A CN 113461875 B CN113461875 B CN 113461875B
Authority
CN
China
Prior art keywords
monomer
silicon
methacrylate
acrylate
treating agent
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
Application number
CN202110850269.9A
Other languages
Chinese (zh)
Other versions
CN113461875A (en
Inventor
涂伟文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuke New Materials Shanghai Co ltd
Original Assignee
Fuke New Materials Shanghai Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fuke New Materials Shanghai Co ltd filed Critical Fuke New Materials Shanghai Co ltd
Priority to CN202110850269.9A priority Critical patent/CN113461875B/en
Publication of CN113461875A publication Critical patent/CN113461875A/en
Application granted granted Critical
Publication of CN113461875B publication Critical patent/CN113461875B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
    • 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
    • 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
    • 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

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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a silicon-containing treating agent, and a preparation method and application thereof. The surface treating agent composition of the invention can endow the treated substrate with excellent water repellency, soft hand feeling and excellent chalk mark resistance.

Description

Silicon-containing treating agent and preparation and application thereof
Technical Field
The invention belongs to the field of functional silicon-containing materials and preparation and application thereof, and particularly relates to a silicon-containing treating agent and preparation and application thereof.
Background
The fluorine-containing polymer has remarkable advantages in water repellency, oil repellency, stain resistance, corrosion resistance and the like, and can endow the substrate with excellent water repellency and oil repellency. However, such fluoropolymers generally contain perfluoroalkyl groups, especially perfluoroalkyl compounds having more than 8 carbon atoms, with the possibility of generating PFOA by decomposition or metabolism. The accumulation of fluorine-containing compounds in the environment is of concern.
In CN 105765025a surface treatment agent is disclosed, which comprises a non-fluoroacrylate polymer with a hard ester acrylate as monomer. In CN 110114435a surface treatment agent is disclosed, which comprises a non-fluoroacrylate polymer having a hard ester acrylate and vinyl chloride as monomers and a wax. However, these surface treatments have poor water repellency and poor hand and chalk mark resistance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a silicon-containing treating agent, and preparation and application thereof, and overcomes the defects of poor hand feeling and chalk mark resistance in the prior art.
The invention provides a silicon-containing treating agent, which comprises a silicon-containing polymer and a medium;
wherein the silicon-containing polymer has at least a constituent unit based on monomer a and a constituent unit based on S;
the monomer a is (methyl) acrylic ester with alkyl with 12-30 carbon atoms; s is polysiloxane containing-SH.
The monomer a is: dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, docosyl acrylate, docosyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate.
The polysiloxane containing-SH is specifically:
(CH 3 ) 3 Si-O[-Si(CH 3 ) 2 -O] m [-SiO(CH 3 )(R1SH)] n -Si(CH 3 ) 3 wherein R1 is an alkylene group having 1 to 3 carbon atoms, m, n is an integer of 1 to 200; wherein the equivalent weight of the functional group of R1SH in the polysiloxane containing-SH is 1900-30000g/mol.
Further, the polysiloxane containing-SH is KF-2001, KF-2004, wherein the functional group equivalent of-R1 SH in KF-2001 is 1900g/mol; the functional group equivalent of-R1 SH in KF-2004 was 30000g/mol.
Further, m and n are integers of 1 to 100.
Further preferably, the monomer a is: one or more of stearyl acrylate, stearyl methacrylate, behenyl acrylate and behenyl methacrylate.
The silicon-containing polymer also has constituent units based on monomer b and/or constituent units based on monomer c; wherein monomer b is a halogenated olefin and monomer c is a monomer having a crosslinkable functional group.
The monomer b is: vinyl chloride, vinylidene chloride, vinyl fluoride, chlorotrifluoroethylene, tetrafluoroethylene, vinylidene fluoride; monomer c is: hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 2-butanone oxime adduct of 2-isocyanatoethyl acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl methacrylate, 3, 5-dimethylpyrazole adduct of 2-isocyanatoethyl acrylate, 3, 5-dimethylpyrazole adduct of 2-isocyanatoethyl methacrylate, diacetone acrylamide, glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxymethacrylate, acetoacetoxy methacrylate.
Further preferably, the monomer b is: vinyl chloride, vinylidene chloride; the monomer c is: 2-butanone oxime adduct of 2-isocyanatoethyl acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl methacrylate, 3, 5-dimethylpyrazole adduct of 2-isocyanatoethyl acrylate, 3, 5-dimethylpyrazole adduct of 2-isocyanatoethyl methacrylate, diacetone acrylamide, glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxylmethacrylate, acetoacetoxy methacrylate.
The total mass percentage of the monomer a, the monomer b, the monomer c and the S is 100%, wherein the monomer a is 50-90%, the monomer b is 0-30%, the monomer c is 0-10%, and the S is 0.01-20%.
It is further preferable that the total mass percentage of the monomer a, the monomer b, the monomer c and the S is 100%, wherein the monomer a is (60 to 80%), the monomer b is (10 to 20%), the monomer c is (1 to 5%), and the S is (1 to 15%).
The mass average molecular weight Mw of the silicon-containing polymer is 5000-500000.
The medium is water or solvent; the medium may be used in any range with respect to 100 parts by mass of the monomer; the silicon-containing treating agent further comprises a surfactant and/or a polymer initiator.
The solvent is as follows: acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, isopropanol may be used in an amount of 1 to 50% by weight, for example, 5 to 45 parts by weight, and particularly preferably 20 to 35 parts by weight, relative to 100 parts by weight of the monomer. The surfactant comprises a nonionic surfactant and a cationic surfactant. The surfactant may be composed of only a nonionic surfactant and a cationic surfactant, or may contain other surfactants, and examples of the other surfactants are amphoteric surfactants, and the surfactant preferably does not contain an anionic surfactant. The cationic surfactants are exemplified by: dodecyl trimethyl ammonium acetate, dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, (dodecyl methyl benzyl) trimethyl ammonium chloride, benzyl dodecyl dimethyl ammonium chloride, methyl dodecyl di (hydrogen polyoxyethylene) ammonium chloride, benzyl dodecyl di (hydrogen polyoxyethylene) ammonium chloride. The amphoteric surfactant is exemplified by: lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethylaminoethyl betaine, fatty amidopropyl dimethylaminoacetic acid betaine. The nonionic surfactant may be exemplified by: polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene glycerol fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkyl alcohol amide, alkyl alkanolamide, alkyne diol, an ethylene oxide adduct of alkyne diol, polyethylene glycol polypropylene glycol block copolymer. The total amount of the surfactants may be 0.05 to 20% by weight, for example 0.2 to 15% by weight, based on 100 parts by weight of the monomer. The weight ratio of nonionic surfactant to cationic surfactant may be from 85:15 to 20:80, more preferably from 80:20 to 40:60. The polymerization initiator may be exemplified by: benzoyl peroxide, lauroyl peroxide, acetyl peroxide, t-butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-hydroxy propionyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium peroxide, ammonium persulfate, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumyl hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate. The polymerization initiator is preferably: the azo diisobutylamidine dihydrochloride may be used in a range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
Note that: the monomer (S) described above are 100 parts by weight, and the monomer (S) are the monomer (S) a, the monomer (S) b, the monomer (S) c and the monomer (S) S.
The preparation method of the silicon-containing treating agent comprises the following steps:
monomers a, b, c and S are polymerized in a medium under the conditions of a surfactant and a polymerization initiator.
The invention provides an application of a silicon-containing treating agent, such as imparting excellent water repellency and antifouling property to fiber products (such as carpets), paper, non-woven fabrics, stone materials, electrostatic filters, dust covers and parts of fuel cells.
Advantageous effects
The water-repellent and oil-repellent composition of the present invention has excellent water repellency, wash durability, soft hand feel, and excellent chalk mark resistance.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
(1) Raw materials
StA stearyl acrylate (purchased from Sigma-Aldrich)
BeA behenyl acrylate (from Sigma-Aldrich)
LA lauryl acrylate (purchased from Sigma-Aldrich)
IBOMA: isobornyl methacrylate (from Sigma-Aldrich)
VCM vinyl chloride (from Sigma-Aldrich)
HEMA hydroxyethyl methacrylate (purchased from Sigma-Aldrich)
DPG dipropylene glycol (from Sigma-Aldrich)
ODAC octadecyl trimethyl ammonium chloride (70% by mass) (ex Sigma-Aldrich)
MOA-15 fatty alcohol-polyoxyethylene ether (from Sigma-Aldrich)
L-43 ethylene oxide propylene oxide Polymer (from Sigma-Aldrich)
L-SH n-dodecyl mercaptan (purchased from Sigma-Aldrich)
KF-2001: mercapto-modified polysiloxane (viscosity: 200 mm) 2 S) (Xinyue chemical industry Co., ltd.)
KF-2004 mercapto-modified polysiloxane (viscosity: 300 mm) 2 S) (Xinyue chemical industry Co., ltd.)
KF-2012 polysiloxane having methacryloyl groups at one end (60 mm) 2 S) (Xinyue chemical industry Co., ltd.)
Figure BDA0003182108000000041
m＝60。
Wax (No. 58) (from Sigma-Aldrich)
V-50 azobisisobutylether hydrochloride (manufactured by Wako pure chemical industries, ltd.).
(2) Test criteria and methods involved in the examples
Spray test
The test cloths were evaluated for water repellency by reference to the AATCC-22 spray method. For a part of the test cloths, the test cloths were obtained by washing 10 times (HL 10) or 20 times (HL 20) according to the home washing method described in ATCC-135 and drying them at 60℃for 30 minutes. The water repellency is represented by water repellency No. (shown in table 1 described below). At the same level, the higher water repellency is indicated by "+" and the lower water repellency is indicated by "-".
Rainfall test
Rainfall tests (bundsmen test) were performed by the method described in IS 0-9865. The rainfall times were 1 minute, 5 minutes and 10 minutes. The evaluation method was similar to the spray test, and the water repellency was represented by water repellency No. (shown in table 1 described below). At the same level, the higher water repellency is indicated by "+" and the lower water repellency is indicated by "-". The amount of rain leakage (g) and the water absorption (%) at 10 minutes of the rainfall test were measured.
TABLE 1
Waterproof No. Status of
100 The surface is not wet, and no water drops are attached
90 Water droplets with non-wetting surfaces but less adhesion
80 The surface exhibits less individual water-drop wetting
70 Half of the surface is wetted and exhibits a smaller, individually wetted, cloth-impermeable state
50 The surface as a whole exhibits wetting
0 The surface and back surfaces are integrally wetted
Evaluation of hand feel
The following 5-scale sensory evaluation was performed by 10 test persons, and the average value was recorded as a hand scale. At the same scale, the hand is indicated as +when softer and-when harder.
5: very soft;
4: softening;
3: the same as untreated test specimen;
2: hard;
1: is very hard.
Chalk mark resistance test
After the test cloth was pressed and slid by a plastic rod having a diameter of 5mm at the front end, whether or not a trace was left on the test cloth was visually observed (chalk mark test), and the test cloth was evaluated according to the following 5 grades.
5: no trace at all;
4: almost no trace was seen;
3: a few traces were visible;
2: visible traces;
1: obvious traces were visible.
Example 1
StA (75 g), HEMA (5 g), KF-2001 (5 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) are added into a high-pressure reaction kettle, and are sheared and dispersed for 5 minutes at a high speed at 60 ℃, and homogenized for 3 times by a high-pressure homogenizer at 40MPa. The autoclave was purged with nitrogen, VCM (15 g) and V-50 (0.3 g) were added thereto, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with heat preservation, whereby a silicon-containing copolymer emulsion S-1 was obtained. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Example 2
StA (70 g), HEMA (5 g), KF-2001 (10 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) are added into a high-pressure reaction kettle, and are sheared and dispersed for 5 minutes at a high speed at 60 ℃, homogenized for 3 times by a high-pressure homogenizer, and the pressure is 40MPa. The autoclave was purged with nitrogen, VCM (15 g) and V-50 (0.3 g) were added, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with heat preservation, to give a silicon-containing copolymer emulsion S-2. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Example 3
StA (65 g), HEMA (5 g), KF-2001 (15 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) are added into a high-pressure reaction kettle, and are sheared and dispersed for 5 minutes at a high speed at 60 ℃, and homogenized for 3 times by a high-pressure homogenizer at 40MPa. The autoclave was purged with nitrogen, VCM (15 g) and V-50 (0.3 g) were added, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with heat preservation, to obtain a silicon-containing copolymer emulsion S-3. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Example 4
StA (70 g), HEMA (5 g), KF-2004 (10 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) were added to a high-pressure reaction vessel, and the mixture was subjected to high-speed shearing and dispersion at 60℃for 5 minutes, and homogenized 3 times by a high-pressure homogenizer under a pressure of 40MPa. The autoclave was purged with nitrogen, VCM (15 g) and V-50 (0.3 g) were added, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with heat preservation, to give a silicon-containing copolymer emulsion S-4. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Example 5
BeA (70 g), HEMA (5 g), KF-2001 (10 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) are added into a high-pressure reaction kettle, and are sheared and dispersed for 5 minutes at a high speed at 60 ℃, homogenized for 3 times by a high-pressure homogenizer, and the pressure is 40MPa. The autoclave was purged with nitrogen, VCM (15 g) and V-50 (0.3 g) were added, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with heat preservation, to give a silicon-containing copolymer emulsion S-5. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Example 6
StA (60 g), LA (10 g), HEMA (5 g), KF-2001 (10 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) are added into a high-pressure reaction kettle, sheared and dispersed for 5 minutes at a high speed at 60 ℃, and homogenized for 3 times by a high-pressure homogenizer at 40MPa. The autoclave was purged with nitrogen, VCM (15 g) and V-50 (0.3 g) were added, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with heat preservation, to give a silicon-containing copolymer emulsion S-6. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Example 7
StA (62.7 g), IBOMA (7.3 g), HEMA (5 g), KF-2001 (10 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) are added into a high-pressure reaction kettle, and are sheared and dispersed for 5 minutes at a high speed at 60 ℃, homogenized for 3 times by a high-pressure homogenizer at 40MPa. The autoclave was purged with nitrogen, VCM (15 g) and V-50 (0.3 g) were added, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with heat preservation, to obtain a silicon-containing copolymer emulsion S-7. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Example 8
StA (60 g), beA (7.1 g), LA (3.8 g), IBOMA (4.5 g), HEMA (5 g), KF-2001 (10 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) are added into a high-pressure reaction kettle, and the mixture is sheared and dispersed for 5 minutes at a high speed at 60 ℃, homogenized for 3 times by a high-pressure homogenizer, and the pressure is 40MPa. The autoclave was purged with nitrogen, VCM (15 g) and V-50 (0.3 g) were added thereto, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with heat preservation, whereby a silicon-containing copolymer emulsion S-1 was obtained. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Comparative example 1
StA (80 g), HEMA (5 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) are added into a high-pressure reaction kettle, and the mixture is sheared and dispersed for 5 minutes at a high speed at 60 ℃, homogenized for 3 times by a high-pressure homogenizer, and the pressure is 40MPa. The autoclave was purged with nitrogen, and VCM (15 g), L-SH (0.1 g) and V-50 (0.3 g) were added thereto, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with maintaining the temperature to obtain copolymer emulsion N-1. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Comparative example 2
BeA (80 g), HEMA (5 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) are added into a high-pressure reaction kettle, and high-speed shearing and dispersing are carried out for 5 minutes at 60 ℃, and the mixture is homogenized for 3 times by a high-pressure homogenizer at 40MPa. The autoclave was purged with nitrogen, and VCM (15 g), L-SH (0.1 g) and V-50 (0.3 g) were added thereto, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with maintaining the temperature to obtain copolymer emulsion N-2. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Comparative example 3
StA (43.2 g), beA (36.8 g), HEMA (5 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) were added to a high-pressure reaction vessel, and the mixture was subjected to high-speed shearing and dispersion at 60℃for 5 minutes, and homogenized 3 times by a high-pressure homogenizer at 40MPa. The autoclave was purged with nitrogen, and VCM (15 g), L-SH (0.1 g) and V-50 (0.3 g) were added thereto, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with maintaining the temperature to obtain copolymer emulsion N-3. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Comparative example 4
StA (36.7 g), beA (27.3 g), LA (5.8 g), IBOMA (10.5 g), HEMA (5 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) are added into a high-pressure reaction kettle, sheared and dispersed for 5 minutes at a high speed at 60 ℃, homogenized for 3 times by a high-pressure homogenizer, and the pressure is 40MPa. The autoclave was purged with nitrogen, and VCM (15 g), L-SH (0.1 g) and V-50 (0.3 g) were added thereto, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with maintaining the temperature to obtain copolymer emulsion N-4. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Comparative example 5
StA (70 g), KF-2012 (10 g), (36.8 g), HEMA (5 g), water (193.25 g), DPG (27.5 g), ODAC (5 g), MOA-15 (2 g) and L-43 (0.75 g) are added into a high-pressure reaction kettle, sheared and dispersed for 5 minutes at a high speed at 60 ℃, and homogenized for 3 times by a high-pressure homogenizer at 40MPa. The autoclave was purged with nitrogen, VCM (15 g) and V-50 (0.3 g) were added, and the temperature was gradually raised to 65℃and the reaction was continued for 5 hours with heat preservation, whereby copolymer emulsion N-5 was obtained. The solids content was adjusted to 30% with water again. The composition of the copolymer obtained is substantially identical to the composition of the monomers added.
Table 2 test results of the test cloths after treatment
Figure BDA0003182108000000091

Claims (8)

1. A silicon-containing treating agent, characterized in that the treating agent component comprises a silicon-containing polymer, a medium;
wherein the silicon-containing polymer has at least a constituent unit based on monomer a and a constituent unit based on S;
the monomer a is (methyl) acrylic ester with alkyl with 12-30 carbon atoms; s is polysiloxane containing-SH; wherein the polysiloxane containing-SH is specifically (CH) 3 ) 3 Si-O[-Si(CH 3 ) 2 -O] m [-SiO(CH 3 )(R1SH)] n -Si(CH 3 ) 3 Wherein R1 is an alkylene group having 1 to 3 carbon atoms, m and n are each an integer of 1 to 200; the silicon-containing polymer also has a constituent unit based on monomer b and a constituent unit based on monomer c; wherein monomer b is vinyl chloride and monomer c is a monomer having a crosslinkable functional group; the total mass percentage of the monomer a, the monomer b, the monomer c and the monomer S is 100%, wherein the monomer a is 50-90%, the monomer b is 0-30%, the monomer c is 0-10%, the S is 0.01-20%, and the dosage of the monomer b and the monomer c is not 0.
2. The silicon-containing treating agent according to claim 1, wherein the monomer a is: one or more of dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, docosyl acrylate, docosyl methacrylate, isobornyl acrylate and isobornyl methacrylate.
3. The silicon-containing treating agent according to claim 1, wherein the monomer c is: hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, diacetone acrylamide, glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, acetoacetoxy methacrylate.
4. The silicon-containing treatment agent according to claim 1, wherein the mass average molecular weight Mw of the silicon-containing polymer is 5000 to 500000.
5. The silicon-containing treating agent according to claim 1, wherein the medium is water and a solvent; the solvent is as follows: one or more of acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and isopropanol, wherein the dosage of the one or more of the acetone, the methyl ethyl ketone, the ethyl acetate, the propylene glycol, the dipropylene glycol monomethyl ether, the dipropylene glycol, the tripropylene glycol, the ethanol and the isopropanol is 1-50 parts by weight relative to 100 parts by weight of the monomer; the silicon-containing treating agent further includes a surfactant and a polymer initiator.
6. The silicon-containing treating agent according to claim 5, wherein the surfactant is a nonionic surfactant and a cationic surfactant; the polymer initiator is as follows: benzoyl peroxide, lauroyl peroxide, acetyl peroxide, tert-butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-hydroxy propionyl peroxide, azo diisobutyl amidine dihydrochloride, azo diisobutyronitrile, sodium peroxide, potassium peroxide, ammonium persulfate, di-tert-butyl peroxide, cumyl hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate; the polymerization initiator is used in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.
7. A method of producing the silicon-containing treating agent as claimed in any one of claims 1 to 6, comprising:
monomers a, b, c and S are polymerized in a medium under the conditions of a surfactant and a polymerization initiator.
8. Use of the silicon-containing treating agent as claimed in any one of claims 1 to 6 as a water-repellent and oil-repellent agent.
CN202110850269.9A 2021-07-27 2021-07-27 Silicon-containing treating agent and preparation and application thereof Active CN113461875B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110850269.9A CN113461875B (en) 2021-07-27 2021-07-27 Silicon-containing treating agent and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110850269.9A CN113461875B (en) 2021-07-27 2021-07-27 Silicon-containing treating agent and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN113461875A CN113461875A (en) 2021-10-01
CN113461875B true CN113461875B (en) 2023-05-19

Family

ID=77882760

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110850269.9A Active CN113461875B (en) 2021-07-27 2021-07-27 Silicon-containing treating agent and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN113461875B (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01168971A (en) * 1987-12-23 1989-07-04 Nisshin Kagaku Kogyo Kk Elastic processing agent for fiber and feeling-improving agent
KR100714328B1 (en) * 2003-01-27 2007-05-04 다이킨 고교 가부시키가이샤 Coating Composition
KR101248707B1 (en) * 2008-03-31 2013-03-28 다우 코닝 코포레이션 Dispersion of fluorosilicones and fluorine- and silicon-containing surface treatment agent
ES2573944T3 (en) * 2008-09-15 2016-06-13 Daikin Industries, Ltd. Fluorosilicone polymers and surface treatment agent
CN109923190B (en) * 2016-12-15 2022-03-01 大金工业株式会社 Water-drawing agent
EP3757187A4 (en) * 2018-02-20 2021-10-27 Daikin Industries, Ltd. Surface treatment agent

Also Published As

Publication number Publication date
CN113461875A (en) 2021-10-01

Similar Documents

Publication Publication Date Title
CN109923190B (en) Water-drawing agent
JP4927760B2 (en) Fluorosilicone and fluorine-containing silicon-containing surface treatment agent
JP5546459B2 (en) Fluorosilicone dispersion and fluorine-containing silicon-containing surface treatment agent
EP3315578B1 (en) Water repellent composition, method for producing water repellent composition, and article
US6979711B2 (en) Fluorine efficient finishes for textiles
CN108699426B (en) Surface treating agent
JP5529121B2 (en) Aqueous polymer dispersion composition and surface treatment agent
KR20080044833A (en) Polymeric extenders for surface effects
JP6870093B2 (en) Water repellent composition
JP2022111181A (en) Surface treatment agent
WO2015076348A1 (en) Water-based surface treatment agent
KR102650932B1 (en) Fluoropolymers and surface treatment agents
JP2007270378A (en) Fiber product processed to be water repellent, oil repellent and soil free, and processing method thereof
JP2023100627A (en) Water-repellent softener
KR20210084436A (en) Water and oil repellent composition, water and oil repellent treatment method, and water and oil repellent fiber
JP5569614B2 (en) Aqueous emulsion composition
CN113461875B (en) Silicon-containing treating agent and preparation and application thereof
JP2017066325A (en) Surface preparation agent
CN1318505C (en) Aqueous emulsion composition
CN113494024A (en) Fluorine-silicon-containing treating agent and preparation and application thereof
CN115029928A (en) Water-repellent and oil-repellent agent composition and preparation method and application thereof
CN118834336A (en) Fluorine-containing polymer and water-repellent alcohol-resistant fluorosilicone surface treatment agent
CN115897238A (en) Waterproof and oilproof emulsion for textile and preparation method thereof
KR20240068651A (en) Polymer for water repellent, water repellent composition and water repellent treatment material
KR20240144468A (en) Water-repellent softening agent

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