CN112646118A - Preparation method of fluorine-free water splashing agent for polyurethane - Google Patents
Preparation method of fluorine-free water splashing agent for polyurethane Download PDFInfo
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- CN112646118A CN112646118A CN202011555656.1A CN202011555656A CN112646118A CN 112646118 A CN112646118 A CN 112646118A CN 202011555656 A CN202011555656 A CN 202011555656A CN 112646118 A CN112646118 A CN 112646118A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 19
- 239000004814 polyurethane Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 239000005871 repellent Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 14
- 229920002545 silicone oil Polymers 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 26
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 14
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- PULCKIYKBGOTTG-UHFFFAOYSA-N n-(2,4-dimethylpentan-3-ylidene)hydroxylamine Chemical compound CC(C)C(=NO)C(C)C PULCKIYKBGOTTG-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 238000007086 side reaction Methods 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002940 repellent Effects 0.000 abstract description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 239000004753 textile Substances 0.000 description 9
- 229920002313 fluoropolymer Polymers 0.000 description 5
- 239000004811 fluoropolymer Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of a fluorine-free water-splashing agent for polyurethane. By adopting the polymerized silicone oil polyalcohol with two functional groups as a main material, the fluorine polymer is avoided being used as a raw material for reaction, so that the water repellent prepared by the method is a fluorine-free water repellent which is more environment-friendly compared with the traditional water repellent, and the problem that the traditional water repellent can pollute the environment is solved.
Description
Technical Field
The invention relates to the technical field, in particular to a preparation method of a fluorine-free water splashing agent for polyurethane.
Background
Polyurethane is short for polyurethane and is a high molecular compound. Polyurethane resins have many excellent properties, such as good elasticity and wind resistance, and therefore are widely used in many industries. Although having various advantages, since polyurethane is mainly manufactured using polyester and polyethylene, there is a weak link in decomposing moisture. Therefore, the water repellent is added to compensate for the disadvantage.
The water-splashing agent is widely applied to the clothing industry due to the oleophobic and hydrophobic properties of the water-splashing agent, the traditional water-splashing agent contains fluoropolymer, and the fluoropolymer is an artificially synthesized chemical substance. After the textile is coated with the polyurethane containing the water splashing agent, a compact surface layer can be formed on the surface of the textile, and the extremely low surface can make water or oil difficult to be compatible, so that the textile has the properties of water resistance and oil resistance, and meanwhile, the textile still has good air permeability and soft hand feeling, so that the polyurethane using the water splashing agent is widely applied.
However, the conventional water repellent is not environmentally friendly since it uses a fluoropolymer. The fluoropolymer can generate highly toxic gas after combustion, and certain potential safety hazard also exists. Therefore, it is necessary to find a water repellent agent containing no fluoropolymer to replace the conventional fluorine-containing water repellent agent, so as to achieve more environmental protection on the premise of ensuring that the properties of the textile are not changed.
Disclosure of Invention
The applicant provides a preparation method of a fluorine-free water-splashing agent for polyurethane aiming at the defects in the prior art, so that the environment can be protected by preparing the fluorine-free water-splashing agent which is more environment-friendly.
The technical scheme adopted by the invention is as follows:
a preparation method of a fluorine-free water splashing agent for polyurethane comprises the following steps:
(A) putting 340-360 parts of a main material A and 105-123 parts of a control agent B into a reaction kettle with the temperature of 20-30 ℃ in the kettle in parts by weight, uniformly stirring the main material A and the control agent B by a stirrer arranged in the stirring kettle, and raising the temperature of the reaction kettle to 40-47 ℃ after uniform stirring; the main material A is polymerized silicone oil polyol with two functional groups, the molecular weight of the polymerized silicone oil polyol is 1000-2000, and in fact, the polymerized silicone oil polyol with two functional groups can be used as the main material A of the invention, but a silicon base must be grafted on a branched chain of the polymerized silicone oil polyol adopted in the invention, most of the main chains of the polymerized silicone oil polyol generally have the silicon base, but the main chain of the polymerized silicone oil polyol adopted in the invention can also not have the silicon base;
(B) after the temperature in the reaction kettle is stable, adding a main material C into the reaction kettle, after the main material C is added, raising the temperature in the reaction kettle to 65-75 ℃, and after the temperature in the reaction kettle is stable, keeping the reaction for 50-60 minutes; the main material C is one or more of diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), m-Xylylene Diisocyanate (XDI) and hydroxyethyl acrylate (2-HEA);
(C) adding 0.1-0.4 part of organic bismuth catalyst (bismuth catalyst) into a reaction kettle, reducing the temperature of the reaction kettle to 50-60 ℃, and keeping the reaction for 50-60 minutes after the temperature in the reaction kettle is stable in order to control the reaction more easily during temperature reduction;
(D) adding 3.7-4.4 parts of cross-linking agent D and 99.5-117.1 parts of control agent B into a reaction kettle, stirring for 30-40 minutes by using a stirrer arranged in the stirring kettle, detecting the content of isocyanate group (NCO-) in the mixture in the stirring kettle after stirring is finished, continuing stirring if the content of the isocyanate group (NCO-) in the mixture is higher than 4.3% (mass ratio), stopping stirring until the content of the isocyanate group (NCO-) in the mixture is 3.9-4.3% (mass ratio), and reducing the temperature in the reaction kettle to 45-55 ℃; the crosslinking agent D is one of 1,4 butanediol (1,4BD), 1,6 hexanediol (1,6HD), Trimethylolpropane (TMP) and Ethylene Glycol (EG);
(E) putting 2.8-3.5 parts of Trimethylolpropane (TMP) in total by weight into the reaction kettle for several times, keeping the reaction for 90-120 minutes after the putting is finished, and detecting the content of isocyanate group (NCO-) of the mixture in the stirring kettle;
(F) when the content of the isocyanate group (NCO-) in the mixture is between 2 and 3 percent (mass ratio), 50.2 to 59.1 parts of phenyltributylketoximino silane (Methyl ethyl ketoxim) is added into the reaction kettle and is taken as a bridging agent, so that the phenyl tributylketoximino silane (Methyl ethyl ketoxim) can perform a sealing reaction with the residual isocyanate group (NCO-) in the reaction kettle, and the residual isocyanate group (NCO-) is prevented from performing a side reaction with air.
Further, between the step (A) and the step (B), there is a step (G): and adding 52.1-61.3 parts of diphenylmethane diisocyanate (MDI) into the reaction kettle after the temperature in the reaction kettle is stable, raising the temperature in the reaction kettle to 60-65 ℃ after the adding of the MDI is finished, and keeping the reaction for 50-60 minutes after the temperature in the reaction kettle is stable.
Further, in the step (B), 66 to 77.7 parts of Toluene Diisocyanate (TDI) and 43.7 to 51.5 parts of hydroxyethyl acrylate (2-HEA) are charged into the reaction vessel in the step (B).
Further, the solvent B is a Dimethylformamide (DMF) solvent.
And (E) adding Trimethylolpropane (TMP) into the reaction kettle for three times, adding 1.1 part of the TMP into the reaction kettle for each time, and reacting for 30-40 minutes after each time of adding is finished.
Further, the silicone oil polyol has a molecular weight of 2000.
The invention has the following beneficial effects:
after the textile uses the water repellent agent obtained by the invention, the performance of the textile is unchanged compared with the performance of the traditional water repellent agent, and the fluorine polymer is avoided being used as a reaction raw material in the invention, so the water repellent agent obtained by the invention is a fluorine-free water repellent agent, is more environment-friendly compared with the traditional water repellent agent, and solves the problem that the traditional water repellent agent can pollute the environment.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 shows the performance parameters of polyurethane after the fluorine-free water-repellent agent is added.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings.
A preparation method of a fluorine-free water splashing agent for polyurethane comprises the following steps:
(A) 355.3 g of slioxanes and silicones, di-ME,3- (2-hydroxyethoxy) propyl group-terminated (a polymerized silicone oil polyol with two functional groups, the molecular weight of which is 2000, silicon base is grafted on a branch chain, hereinafter referred to as s-2000) and 118.1 g of Dimethylformamide (DMF) solvent are put into a reaction kettle with the temperature of 25 ℃ in the kettle, the s-2000 and the Dimethylformamide (DMF) solvent are uniformly stirred by a stirrer arranged in the stirring kettle, and the temperature of the reaction kettle is raised to 40 ℃ after uniform stirring;
(G) the method comprises the following steps After the temperature in the reaction kettle is stable, adding 61.3 g of diphenylmethane diisocyanate (MDI) into the reaction kettle, raising the temperature in the reaction kettle to 60 ℃ after the diphenylmethane diisocyanate (MDI) is added, and keeping the reaction for 50 minutes after the temperature in the reaction kettle is stable;
(B) after the temperature in the reaction kettle is stable, 77.7 g of Toluene Diisocyanate (TDI) and 51.1 g of hydroxyethyl acrylate (2-HEA) are added into the reaction kettle, the temperature in the reaction kettle is raised to 70 ℃ after the Toluene Diisocyanate (TDI) and the hydroxyethyl acrylate (2-HEA) are added, and the reaction is kept for 60 minutes after the temperature in the reaction kettle is stable;
(C) adding 0.37 g of organic bismuth catalyst (bismuth catalyst) into a reaction kettle, reducing the temperature of the reaction kettle to 55 ℃, and keeping the reaction for 50-60 minutes;
(D) adding 4.4 g of 1, 4-butanediol (1,4BD) and 117.1 g of Dimethylformamide (DMF) solvent into a reaction kettle, stirring for 30 minutes by using a stirrer arranged in the stirring kettle, detecting the content of isocyanate group (NCO-) of a mixture in the stirring kettle after stirring for 30 minutes, continuing stirring if the content of the isocyanate group (NCO-) in the mixture is higher than 4.3% (mass ratio) until the content of the isocyanate group (NCO-) in the mixture is between 3.9 and 4.3% (mass ratio), stopping stirring, and reducing the temperature in the reaction kettle to 45 ℃; (ii) a
(E) Adding Trimethylolpropane (TMP) with the total weight of 3.3 grams into the reaction kettle for three times, adding 1.1 grams of Trimethylolpropane (TMP) into the reaction kettle every time, keeping the reaction for 30 minutes after the Trimethylolpropane (TMP) is added every time, detecting the content of isocyanate group (NCO-) of the mixture in the stirring kettle after the reaction is finished, and adding the Trimethylolpropane (TMP) into the reaction kettle for three times because the Trimethylolpropane (TMP) contains three functional groups, wherein the Trimethylolpropane (TMP) can better participate in the reaction by adding three times, so that the reaction is convenient to control;
(F) when the content of the isocyanate group (NCO-) in the mixture is between 2 and 3 percent (mass ratio), 59.1 g of phenyltributylketoximino silane (Methyl ethyl ketoxim) is added into the reaction kettle and is used as a bridging agent, so that the phenyl tributylketoximino silane (Methyl ethyl ketoxim) can perform a blocking reaction with the residual isocyanate group (NCO-) in the reaction kettle, and the residual isocyanate group (NCO-) is prevented from performing a side reaction with air.
After the textile uses the water repellent agent obtained by the invention, the performance of the textile is unchanged compared with the performance of the traditional water repellent agent, and the fluorine polymer is avoided being used as a reaction raw material in the invention, so the water repellent agent obtained by the invention is a fluorine-free water repellent agent, is more environment-friendly compared with the traditional water repellent agent, and solves the problem that the traditional water repellent agent can pollute the environment.
The above description is intended to be illustrative and not restrictive, and the scope of the invention is defined by the appended claims, which may be modified in any manner within the scope of the invention.
Claims (6)
1. A preparation method of a fluorine-free water splashing agent for polyurethane comprises the following steps:
(A) putting 340-360 parts of a main material A and 105-123 parts of a control agent B into a reaction kettle with the temperature of 20-30 ℃ in the kettle in parts by weight, uniformly stirring the main material A and the control agent B by a stirrer arranged in the stirring kettle, and raising the temperature of the reaction kettle to 40-47 ℃ after uniform stirring; the main material A is polymerized silicone oil polyol with two functional groups, a silicon base is grafted on a branched chain of the polymerized silicone oil polyol, and the molecular weight of the polymerized silicone oil polyol is 1000-2000;
(B) after the temperature in the reaction kettle is stable, adding a main material C into the reaction kettle, after the main material C is added, raising the temperature in the reaction kettle to 65-75 ℃, and after the temperature in the reaction kettle is stable, keeping the reaction for 50-60 minutes; the main material C is one or more of diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), m-Xylylene Diisocyanate (XDI) and hydroxyethyl acrylate (2-HEA);
(C) adding 0.1-0.4 part of organic bismuth catalyst (bismuth catalyst) into a reaction kettle, reducing the temperature of the reaction kettle to 50-60 ℃, and keeping the reaction for 50-60 minutes after the temperature in the reaction kettle is stable;
(D) adding 3.7-4.4 parts of cross-linking agent D and 99.5-117.1 parts of control agent B into a reaction kettle, stirring for 30-40 minutes by using a stirrer arranged in the stirring kettle, detecting the content of isocyanate group (NCO-) in the mixture in the stirring kettle after stirring is finished, continuing stirring if the content of isocyanate group (NCO-) in the mixture is higher than 4.3% (mass ratio) until the content of isocyanate group (NCO-) in the mixture is 3.9-4.3% (mass ratio), and then reducing the temperature in the reaction kettle to 45-55 ℃; the crosslinking agent D is one of 1,4 butanediol (1,4BD), 1,6 hexanediol (1,6HD), Trimethylolpropane (TMP) and Ethylene Glycol (EG);
(E) putting 2.8-3.3 parts of Trimethylolpropane (TMP) in total by weight into the reaction kettle for several times, keeping the reaction for 90-120 minutes after the putting is finished, and detecting the content of isocyanate group (NCO-) of the mixture in the stirring kettle;
(F) when the content of the isocyanate group (NCO-) in the mixture is between 2 and 3 percent (mass ratio), 50.2 to 59.1 parts of phenyltributylketoximino silane (Methyl ethyl ketoxim) is added into the reaction kettle, so that the residual isocyanate group (NCO-) in the reaction kettle reacts with the phenyltributylketoximino silane (Methyl ethyl ketoxim), and the residual isocyanate group (NCO-) is prevented from carrying out side reaction with air.
2. The method for preparing a fluorine-free water-repellent agent for polyurethane according to claim 1, wherein the method comprises the following steps: between step (A) and step (B) there is also a step (G): and adding 52.1-61.3 parts of diphenylmethane diisocyanate (MDI) into the reaction kettle after the temperature in the reaction kettle is stable, raising the temperature in the reaction kettle to 60-65 ℃ after the adding of the MDI is finished, and keeping the reaction for 50-60 minutes after the temperature in the reaction kettle is stable.
3. The method for preparing a fluorine-free water-repellent agent for polyurethane according to claim 1 or 2, characterized in that: in the step (B), 66-77.7 parts of Toluene Diisocyanate (TDI) and 43.7-51.5 parts of hydroxyethyl acrylate (2-HEA) are charged into a reaction kettle.
4. The method for preparing a fluorine-free water-repellent agent for polyurethane according to claim 1 or 2, characterized in that: the solvent B is a Dimethylformamide (DMF) solvent.
5. The method for preparing a fluorine-free water-repellent agent for polyurethane according to claim 1 or 2, characterized in that: and (E) adding Trimethylolpropane (TMP) into the reaction kettle for three times, adding 1.1 part of the TMP into the reaction kettle each time, and reacting for 30-40 minutes after each time of adding is finished.
6. The method for preparing a fluorine-free water-repellent agent for polyurethane according to claim 1 or 2, characterized in that: the molecular weight of the silicone oil polyol is 2000.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62225516A (en) * | 1986-03-26 | 1987-10-03 | Chisso Corp | Silicone-modified polyurethane and silicone compound for modification |
| US4839443A (en) * | 1987-02-04 | 1989-06-13 | Chisso Corporation | Polysiloxane containing hydroxyl groups and a silicone-modified polyurethane using the same |
| CN104086740A (en) * | 2014-07-09 | 2014-10-08 | 温州柯莱恩科技有限公司 | Method for preparing organic silicon graft modified polyurethane resin for synthetic leather |
| CN105385401A (en) * | 2015-12-26 | 2016-03-09 | 盐城西臣奥勒医疗科技有限公司 | Organic silicone modified polyurethane synthetic adhesive and preparation method thereof |
| CN108003314A (en) * | 2017-12-19 | 2018-05-08 | 传化智联股份有限公司 | A kind of preparation method of amphipathic free radical type polysilicone-polyurethanes prepolymer |
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2020
- 2020-12-24 CN CN202011555656.1A patent/CN112646118A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62225516A (en) * | 1986-03-26 | 1987-10-03 | Chisso Corp | Silicone-modified polyurethane and silicone compound for modification |
| US4839443A (en) * | 1987-02-04 | 1989-06-13 | Chisso Corporation | Polysiloxane containing hydroxyl groups and a silicone-modified polyurethane using the same |
| CN104086740A (en) * | 2014-07-09 | 2014-10-08 | 温州柯莱恩科技有限公司 | Method for preparing organic silicon graft modified polyurethane resin for synthetic leather |
| CN105385401A (en) * | 2015-12-26 | 2016-03-09 | 盐城西臣奥勒医疗科技有限公司 | Organic silicone modified polyurethane synthetic adhesive and preparation method thereof |
| CN108003314A (en) * | 2017-12-19 | 2018-05-08 | 传化智联股份有限公司 | A kind of preparation method of amphipathic free radical type polysilicone-polyurethanes prepolymer |
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Application publication date: 20210413 |