CN118440282A - Polyurea modified organosilicon softener and preparation method thereof - Google Patents
Polyurea modified organosilicon softener and preparation method thereof Download PDFInfo
- Publication number
- CN118440282A CN118440282A CN202410709488.9A CN202410709488A CN118440282A CN 118440282 A CN118440282 A CN 118440282A CN 202410709488 A CN202410709488 A CN 202410709488A CN 118440282 A CN118440282 A CN 118440282A
- Authority
- CN
- China
- Prior art keywords
- polyurea modified
- softener
- silicone oil
- amino
- polyurea
- 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.)
- Pending
Links
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920002545 silicone oil Polymers 0.000 claims abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 6
- 229920000570 polyether Polymers 0.000 claims abstract description 6
- 239000011550 stock solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003995 emulsifying agent Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004902 Softening Agent Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- -1 hydrogen compound Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- FKNSOURYLWWLDY-UHFFFAOYSA-N 1-[2-(dimethylamino)ethyl-methylamino]ethanol Chemical compound CC(O)N(C)CCN(C)C FKNSOURYLWWLDY-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- SBAJRGRUGUQKAF-UHFFFAOYSA-N 3-(2-cyanoethylamino)propanenitrile Chemical compound N#CCCNCCC#N SBAJRGRUGUQKAF-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- OVWMLAPGHWXVDA-UHFFFAOYSA-N CC(C(CCCN(C)C)CCCN(C)C)(N)O Chemical compound CC(C(CCCN(C)C)CCCN(C)C)(N)O OVWMLAPGHWXVDA-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003999 initiator Substances 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
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- ZIKLHFPNSYDZSP-UHFFFAOYSA-N 1-n-(2-aminoethyl)-2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CNCCN ZIKLHFPNSYDZSP-UHFFFAOYSA-N 0.000 claims 1
- CRZVCXRSZLYXAL-UHFFFAOYSA-N 2-[1-(dimethylamino)propan-2-yl-methylamino]ethanol Chemical compound CN(C)CC(C)N(C)CCO CRZVCXRSZLYXAL-UHFFFAOYSA-N 0.000 claims 1
- 150000002009 diols Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 239000004744 fabric Substances 0.000 abstract description 10
- 238000005406 washing Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 239000004671 silicon softener Substances 0.000 abstract description 2
- 239000004753 textile Substances 0.000 description 18
- 229920013822 aminosilicone Polymers 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000013329 compounding Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- WFHALSLYRWWUGH-UHFFFAOYSA-N 2,3-dimethylpent-2-ene Chemical group CCC(C)=C(C)C WFHALSLYRWWUGH-UHFFFAOYSA-N 0.000 description 1
- DCULKBZETKTADO-UHFFFAOYSA-N 5,5-dimethylhex-3-en-1-ol Chemical group CC(C)(C)C=CCCO DCULKBZETKTADO-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G18/3271—Hydroxyamines
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/653—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain modified by isocyanate compounds
-
- 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)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a polyurea modified organosilicon softener and a preparation method thereof. The preparation method of the polyurea modified organosilicon softener is synthesized by adopting a one-pot method, so that the process steps are reduced, the process flow is simplified, and the process equipment is reduced; according to the polyurea modified organic silicon softener, the polyurea groups are introduced into the silicone oil chain segments, the elasticity characteristics of the polyurea groups increase the stiff and elastic handfeel of the softener, the influence of repeated washing on the handfeel effect is reduced, and meanwhile, polyether glycol, polyester glycol and special fatty chains are adopted as end capping agents, so that the characteristics of hydrophilicity, adhesive force and the like of fabrics can be increased, and the use effect of the fabrics on different scenes is improved.
Description
Technical Field
The invention relates to the technical field of fine chemical preparation and application, in particular to a polyurea modified organosilicon softener and a preparation method thereof.
Background
Polyurea is an elastomeric material formed by the reaction of an isocyanate component with an amino compound component. Due to its urea groupsThe physical properties of the polyurethane are superior to those of polyurethane in terms of adhesion and mechanical strength.
Textile auxiliaries are fine chemicals which are necessary in textile production processes. The textile auxiliary has an indispensable important effect on improving the product quality and the added value of textiles, can endow the textiles with various special functions and styles, such as softness, crease resistance, shrink resistance, water resistance, antibiosis, antistatic, flame retardance and the like, can improve dyeing and finishing processes, and has the effects of saving energy sources and reducing processing cost. Textile auxiliaries are critical to the overall level of the textile industry and to their role in the textile industry chain. Among them, organosilicon is an assistant widely used in textile industry, which has unique characteristics and advantages and can improve the performance and quality of textiles.
In the prior art, as an important softener in textile auxiliaries, the main components of the softener are mainly a block silicone oil system and amino silicone oil, the structure is relatively simple, the provided hand feeling effect is single, and the continuous pursuit of people on textile experience is difficult to be satisfied; secondly, in order to enrich the hand feeling effect, a mode of compounding a plurality of compounds is adopted, so that the compatibility among different substances is solved, and the problems of the compatibility of the emulsifying agent and the emulsifying agent, the dosage of the emulsifying agent and the like are also considered; and the hand feeling effect is improved by adopting rich compounding, which relates to multi-step operation, thus reducing the efficiency and increasing the cost.
Disclosure of Invention
The invention aims to provide a polyurea modified organosilicon softener and a preparation method thereof, which solve the problems that the structure is relatively simple and the hand feeling effect is single when the main components in the prior art are a block silicone oil system and amino silicone oil; the mode of compounding various compounds is limited by compatibility, and the compounding of various compounds involves multi-step operation, so that the problems of efficiency reduction and cost increase are caused, and the defects of the prior art are overcome.
The invention provides a preparation method of a polyurea modified organosilicon softening agent, which comprises the following steps:
S1: adding a blocking agent into amino-terminated silicone oil, and dehydrating in vacuum until the water content is less than or equal to 100ppm;
s2: adding with stirring and isocyanate, heating to 40-140 ℃ and preserving heat for 1-24h, and continuing until all isocyanate groups react, wherein the reaction formula is as follows:
Wherein m 1 and m 2 are integers of 1-50, L is hydrogen or alkyl, X is polymerization degree, YH 2 is an initiator for synthesizing polyether glycol;
s3: adding acid and a dispersing solvent to terminate all the reactions to obtain a polyurea modified organosilicon softener stock solution;
S4: adding the emulsifier to disperse at a high speed of 1500-2000rpm, and gradually adding deionized water to obtain the emulsion-state polyurea modified organosilicon softener.
Further, the amino-terminated silicone oil is synthesized by the following steps:
S11, adding a catalyst accounting for 0.06 percent of the total mass of the diamino seal agent and the reaction materials into methyl cyclosiloxane with stirring, heating to 105 ℃ and preserving heat for more than 2 hours;
s12: after detecting that the solid content is more than or equal to 88 percent by an infrared rapid moisture meter, heating to 140-150 ℃ to break media;
S13: and continuously vacuumizing at the vacuum degree of-0.09-0.1 MPa until the content of the solid matters detected by an infrared rapid moisture meter is more than or equal to 98%, and cooling and stopping vacuumizing to obtain amino-terminated silicone oil.
Further, the molecular weight of the amino-terminated silicone oil is M, the molecular weight of the diamino seal agent is T, the synthesis yield of the amino-terminated silicone oil is N, the addition mass of the methylcyclosiloxane is (M-T)/N, and the catalyst is 50% of an ethanol solution of tetramethyl ammonium hydroxide.
Further, in the stock solution, the amino-terminated silicone oil accounts for 22.59-65.82%, the end capping agent accounts for 1.17-45.17%, the isocyanate accounts for 1.9-5.25%, the acid accounts for 0.34-1.28%, the dispersion solvent accounts for 30%, and the mass ratio of the emulsifier, deionized water to the stock solution is 0.2:2.8:1.
Further, the end capping agent is dihydric alcohol and/or monofunctional active hydrogen compound.
Further, the dihydric alcohol is at least one of polyethylene glycol, hydroxyl-terminated block polyether silicone oil, polyethylene glycol adipate glycol, poly-1, 4-butanediol adipate glycol and poly-hexanediol adipate glycol.
Further, the monofunctional active hydrogen compound is at least one of N, N-dimethylethanolamine, bis (2-cyanoethyl) amine, tetrahydropyrrole, tetramethyl-propylene triamine, trimethyl-hydroxyethyl-propylene diamine, N-dimethylaminoethyl-N-methylaminoethanol and bis (3-dimethylaminopropyl) amino isopropanol.
Further, the isocyanate is at least one of hexamethylene diisocyanate, isophorone diisocyanate and diphenylmethane diisocyanate.
Further, the acid is glacial acetic acid, the dispersion solvent is at least one of ethylene glycol butyl ether and diethylene glycol monobutyl ether, and the emulsifier is at least one of AEO series, XL series and TO series.
The invention also provides a polyurea modified organosilicon softener, which is prepared according to the preparation method.
The invention has the following beneficial effects: the preparation method of the polyurea modified organosilicon softener is synthesized by adopting a one-pot method, so that the process steps are reduced, the process flow is simplified, and the process equipment is reduced;
According to the polyurea modified organic silicon softener, the polyurea group is introduced into the silicone oil chain segment, the elasticity of the polyurea group increases the stiff and elastic hand feeling of the softener, the influence of repeated washing on the hand feeling effect is reduced, and meanwhile, polyether glycol, polyester glycol and special fatty chains are adopted as end capping agents, so that the characteristics of hydrophilicity, adhesive force and the like of fabrics can be increased, and the use effect of the fabrics on different scenes is improved.
Detailed Description
The technical solutions of the present application will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments.
The amino-terminated silicone oil adopted in the invention is polydimethylsiloxane, and the end group of the amino-terminated silicone oil is amino, so that a high molecular structure taking Si-O-Si as a main chain is formed; it has lubricity: a thin and stable lubricating film can be formed on the friction surface, so that friction loss is reduced, and the comfort level of the textile is improved; resistance to foam: foam generation is effectively inhibited, and the production process is optimized; thermal stability: the performance can be maintained even under the high-temperature environment, and the method is suitable for textiles treated at high temperature; adsorptivity, compatibility and ease of emulsification: is compatible with various textile assistants, is easy to form stable emulsion, and improves the processing efficiency; application flexibility: can be used alone or combined with other components to meet different processing requirements; improving fabric performance: the elasticity and the hand feeling of the fabric are obviously improved, and the market competitiveness is enhanced; wash fastness: the treated textile has good water resistance and dry cleaning resistance, and maintains a long-term softening effect. Amino terminated silicone oils may be obtained by self-synthesis or commercially available.
In the invention, in order to conveniently obtain amino-terminated silicone oil with different molecular weights, self-synthesis is adopted, and the specific steps are as follows:
S11, adding a catalyst accounting for 0.06 percent of the total mass of the diamino seal agent and the reaction materials into methyl cyclosiloxane with stirring, heating to 105 ℃ and preserving heat for more than 2 hours;
s12: after the infrared rapid moisture meter detects that the solid content is more than or equal to 88 percent, heating to 140-150 ℃ to break the medium (namely the catalyst is decomposed and fails at high temperature);
S13: and continuously vacuumizing at the vacuum degree of-0.09-0.1 MPa until the content of the solid matters detected by an infrared rapid moisture meter is more than or equal to 98%, and cooling and stopping vacuumizing to obtain amino-terminated silicone oil.
When the molecular weight of the required amino-terminated silicone oil is M, the molecular weight of the diamino end-capping agent is T, the synthesis yield of the amino-terminated silicone oil is N, the addition mass of methyl cyclosiloxane is (M-T)/N, the catalyst is 50% of an ethanol solution of tetramethyl ammonium hydroxide, and the diamino end-capping agent is ZC301 (textile auxiliary Co., ltd.).
Among them, the XL series and the TO series of the emulsifier refer TO those of BASF Lutensol.
The dispersing solvent is used for adjusting the viscosity of the stock solution, the emulsifying agent and the deionized water are used for dispersing, diluting and emulsifying the stock solution, and the three are not reaction materials for preparing the stock solution of the polyurea modified organosilicon softener, but the fluidity and the dispersibility of the prepared stock solution are adjusted so as to realize the impregnation effect on the fabric; therefore, when the preparation is carried out by adopting the mutual proportion of amino-terminated silicone oil, the blocking agent, isocyanate and acid, the addition proportion of the dispersing solvent, the emulsifying agent and deionized water can be adjusted according to the actual situation, so that the emulsion-state polyurea modified organosilicon softener with proper viscosity or proper concentration can be obtained.
The specific implementation mode of the polyurea modified amino-terminated silicone oil is as follows:
Example 1
By total mass, 21.39% of polyethylene glycol (Mn=2000) and 0.95% of N, N-dimethylethanolamine are added into 42.78% of double-end amino silicone oil (Mn=4000), vacuum dehydration is carried out until the water content reaches 60ppm, 3.6% of HDI is added along with stirring, the temperature is kept at 90 ℃ for continuous reaction until the peak of isocyanate groups is detected to disappear, 1.28% of glacial acetic acid and 30% of diethylene glycol monobutyl ether are added to obtain a polyurea modified organosilicon softener stock solution, an emulsifier AEO-7 with the mass ratio of 0.2 to the stock solution is added for high-speed dispersion at 1500rpm, and deionized water with the mass ratio of 2.4 to the stock solution is gradually added to obtain the emulsion-state polyurea modified organosilicon softener.
Example 2
31.21% Of polyethylene glycol (Mn=2000) and 1.39% of N, N-dimethylethanolamine are added into 31.21% of double-end amino silicone oil (Mn=4000) by total mass, vacuum dehydration is carried out to a water content of 60ppm, 5.25% of HDI is added along with stirring, the temperature is kept at 90 ℃ for continuous reaction until the peak of isocyanate groups is detected to disappear, 0.94% of glacial acetic acid and 30% of diethylene glycol monobutyl ether are added to obtain a polyurea modified organosilicon softener stock solution, an emulsifier AEO-7 with the mass ratio of 0.2 to the stock solution is added to be dispersed at a high speed at 1600rpm, and deionized water with the mass ratio to the stock solution of 2.4 is gradually added to obtain the emulsion-state polyurea modified organosilicon softener.
Example 3
By total mass, 21.39% of polyethylene glycol adipate glycol (Mn=2000) and 1.39% of N, N-dimethylethanolamine are added into 31.21% of double-end amino silicone oil (Mn=4000), vacuum dehydration is carried out until the water content reaches 60ppm, 5.25% of HDI is added with stirring, the temperature is kept at 90 ℃ for continuous reaction until the peak of isocyanate groups is detected to disappear, 0.94% of glacial acetic acid and 30% of diethylene glycol monobutyl ether are added to obtain a polyurea modified organosilicon softener stock solution, an emulsifier AEO-7 with the mass ratio of 0.2 to the stock solution is added for high-speed dispersion at 1700rpm, and deionized water with the mass ratio to the stock solution of 2.4 is gradually added to obtain the emulsion polyurea modified organosilicon softener.
Example 4
32.77% Of polyethylene glycol (Mn=4000) and 0.73% of N, N-dimethylethanolamine are added into 32.77% of double-end amino silicone oil (Mn=4000) by total mass, vacuum dehydration is carried out to a water content of 60ppm, 2.76% of HDI is added along with stirring, the temperature is kept at 90 ℃ for continuous reaction until the peak of isocyanate groups is detected to disappear, 0.99% of glacial acetic acid and 30% of diethylene glycol monobutyl ether are added to obtain a polyurea modified organosilicon softener stock solution, an emulsifier AEO-7 with the mass ratio of 0.2 to the stock solution is added to be dispersed at a high speed of 1800rpm, and deionized water with the mass ratio to the stock solution of 2.4 is gradually added to obtain the emulsion-state polyurea modified organosilicon softener.
Example 5
Adding 45.17% of polyethylene glycol (Mn=4000) into 22.59% of double-end amino silicone oil (Mn=4000) by total mass, vacuum dehydrating to 40ppm of water content, adding 1.9% of HDI with stirring, keeping the temperature at 90 ℃ for continuous reaction until the peak of isocyanate groups is disappeared, adding 0.34% of glacial acetic acid and 30% of diethylene glycol monobutyl ether to obtain a stock solution of the polyurea modified organosilicon softener, adding an emulsifier AEO-7 with the mass ratio of 0.2 to the stock solution, dispersing at 1900rpm at high speed, and gradually adding deionized water with the mass ratio of 2.4 to the stock solution to obtain the emulsion-state polyurea modified organosilicon softener.
Example 6
Adding 1.17% of N, N-dimethylethanolamine into 65.82% of double-end amino silicone oil (Mn=10000) by total mass, vacuum dehydrating to 40ppm of water content, adding 2.21% of HDI with stirring, continuously reacting at 90 ℃ until the peak of an isocyanate group disappears, adding 0.79% of glacial acetic acid and 30% of diethylene glycol monobutyl ether to obtain a polyurea modified organosilicon softener stock solution, adding an emulsifier AEO-7 with the mass ratio of 0.2 to the stock solution, dispersing at 2000rpm, and gradually adding deionized water with the mass ratio of 2.4 to the stock solution to obtain the emulsion-state polyurea modified organosilicon softener.
Results testing:
The nylon spandex knitted fabric is adopted, finishing liquid containing a corresponding softening agent is used, and the hand feeling is compared and tested after conditioning for 2 hours through padding technology (one padding, one pressing, 2KG pressure, 25m/min speed, setting temperature 160 ℃ and setting time 1 min).
The hand ratings are shown in table 1:
TABLE 1
| Grade 5 | Grade 4 | 3 Grade | Level 2 | Level 1 |
| Very good | Good quality | In (a) | Slightly worse | Difference of difference |
The water washing method comprises the following steps: referring to GB/T8629-2017, a household washing and drying program for textile test is adopted (a C-type standard washing machine is adopted as a washing machine, a standard washing agent 4 is adopted as a washing agent, 4M is adopted as a washing program, no accompanying washing is adopted as a washing program, and an A1 type dryer is adopted as a tumbling dryer).
Performance tests were performed using a control (softener used for the finishing liquor is SILYOUWET T guangdomei silicone limited) and examples 1-6, and the test results are shown in table 2:
TABLE 2
As can be seen from Table 2, the polyurea modified silicone softener of the present invention, because it contains polyurea groups, has a rich and remarkable feel of smoothness, elasticity and stiffness; after washing for many times, the original smooth, elastic and stiff hand feeling of the fabric is less affected, so that the fabric can meet different use scenes and different use requirements.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions, combinations and alterations may be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the polyurea modified organosilicon softener is characterized by comprising the following steps of:
S1: adding a blocking agent into amino-terminated silicone oil, and dehydrating in vacuum until the water content is less than or equal to 100ppm;
s2: adding with stirring and isocyanate, heating to 40-140 ℃ and preserving heat for 1-24h, and continuing until all isocyanate groups react, wherein the reaction formula is as follows:
Wherein m 1 and m 2 are integers of 1-50, L is hydrogen or alkyl, X is polymerization degree, YH 2 is an initiator for synthesizing polyether glycol;
s3: adding acid and a dispersing solvent to terminate all the reactions to obtain a polyurea modified organosilicon softener stock solution;
S4: adding the emulsifier to disperse at a high speed of 1500-2000rpm, and gradually adding deionized water to obtain the emulsion-state polyurea modified organosilicon softener.
2. The method for preparing the polyurea modified organosilicon softening agent according to claim 1, wherein the amino-terminated silicone oil is synthesized by the following steps:
S11, adding a catalyst accounting for 0.06 percent of the total mass of the diamino seal agent and the reaction materials into methyl cyclosiloxane with stirring, heating to 105 ℃ and preserving heat for more than 2 hours;
s12: after detecting that the solid content is more than or equal to 88 percent by an infrared rapid moisture meter, heating to 140-150 ℃ to break media;
S13: and continuously vacuumizing at the vacuum degree of-0.09-0.1 MPa until the content of the solid matters detected by an infrared rapid moisture meter is more than or equal to 98%, and cooling and stopping vacuumizing to obtain amino-terminated silicone oil.
3. The method for preparing the polyurea modified organosilicon softening agent according to claim 2, wherein the molecular weight of the amino-terminated silicone oil is M, the molecular weight of the diamino seal agent is T, the synthesis yield of the amino-terminated silicone oil is N, the addition mass of the methylcyclosiloxane is (M-T)/N, and the catalyst is 50% of an ethanol solution of tetramethylammonium hydroxide.
4. The preparation method of the polyurea modified organosilicon softening agent according to claim 1, wherein the total mass of the stock solution is 22.59-65.82% of amino-terminated silicone oil, 1.17-45.17% of end-capping agent, 1.9-5.25% of isocyanate, 0.34-1.28% of acid, 30% of dispersing solvent and the mass ratio of the emulsifier, deionized water and the stock solution is 0.2:2.8:1.
5. The method for preparing a polyurea modified silicone softener according to claim 4, wherein the end-capping agent is a diol and/or a monofunctional active hydrogen compound.
6. The method for preparing the polyurea modified organosilicon softening agent according to claim 5, wherein the dihydric alcohol is at least one of polyethylene glycol, hydroxyl-terminated block polyether silicone oil, polyethylene glycol adipate glycol, poly-1, 4-butanediol adipate glycol and poly-hexanediol adipate glycol.
7. The method for preparing a polyurea modified silicone softener according to claim 5, wherein the monofunctional active hydrogen compound is at least one of N, N-dimethylethanolamine, bis (2-cyanoethyl) amine, tetrahydropyrrole, tetramethyldiethylenetriamine, trimethylhydroxyethyl propylenediamine, N-dimethylaminoethyl-N-methylaminoethanol, bis (3-dimethylaminopropyl) amino isopropanol.
8. The method for preparing a polyurea modified silicone softener according to claim 4, wherein the isocyanate is at least one of hexamethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate.
9. The method for preparing a polyurea modified silicone softener according TO claim 4, wherein the acid is glacial acetic acid, the dispersion solvent is at least one of ethylene glycol butyl ether and diethylene glycol monobutyl ether, and the emulsifier is at least one of AEO series, XL series and TO series.
10. A polyurea modified silicone softener characterized by being prepared according to the preparation method of any one of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410709488.9A CN118440282A (en) | 2024-06-03 | 2024-06-03 | Polyurea modified organosilicon softener and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410709488.9A CN118440282A (en) | 2024-06-03 | 2024-06-03 | Polyurea modified organosilicon softener and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118440282A true CN118440282A (en) | 2024-08-06 |
Family
ID=92333352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410709488.9A Pending CN118440282A (en) | 2024-06-03 | 2024-06-03 | Polyurea modified organosilicon softener and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118440282A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119431723A (en) * | 2024-11-22 | 2025-02-14 | 广东湛丰精细化工有限公司 | An environmentally friendly polyester modified waterproofing agent and its preparation method and application |
-
2024
- 2024-06-03 CN CN202410709488.9A patent/CN118440282A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119431723A (en) * | 2024-11-22 | 2025-02-14 | 广东湛丰精细化工有限公司 | An environmentally friendly polyester modified waterproofing agent and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101418518A (en) | Method for preparing durable hydrophilic polyether modified amino polysiloxane soft agent | |
| CN118440282A (en) | Polyurea modified organosilicon softener and preparation method thereof | |
| EP1401920A1 (en) | Modified polyorganosiloxanes, aqueous emulsions thereof, their production and their use | |
| CN106750324B (en) | Polyquaternary amino polyether polydimethylsiloxane, preparation method thereof and hand feeling finishing agent | |
| CN111877020B (en) | Modified silicone oil softening agent and preparation method thereof | |
| CN108252104B (en) | Preparation method of textile smoothing agent | |
| CN102634036B (en) | Novel linear amino and polyester modified organosilicon compound for textiles | |
| CN1406297A (en) | Crease resistant finishing of cellulose-containing textiles, and laundry post-treatment agents | |
| CN108611851B (en) | Softening agent emulsion and production process thereof | |
| EP1753906B1 (en) | Textile treatments using fluoropolymer-branched silicone polyethers | |
| CN114855461A (en) | Organic silicon softening agent, preparation method thereof and application thereof in deep color fabric | |
| CN109610177A (en) | A kind of preparation method and application of cationic polyurethane acrylate water repellent | |
| CN112981966B (en) | Comb-shaped association polyurethane composite modified organosilicon softener emulsion and preparation method thereof | |
| CN108547155A (en) | A kind of preparation method of textile softener | |
| CN107189035A (en) | A kind of solvent-free hyperbranched silicone softening agent and preparation method thereof | |
| CN112480414A (en) | Hydrophilic silicone oil and preparation method thereof | |
| CN112981963B (en) | Reticular associative polyurethane composite modified silicone softener emulsion and preparation method thereof | |
| CN114045682B (en) | A smooth and soft additive for cotton package yarn and its preparation method and application | |
| CN117364496A (en) | Preparation method of softening agent with high fluffiness and soft and smooth touch for cotton cloth | |
| CN116791383A (en) | Cotton spinning cloth environment-friendly fixation method based on compound multi-cation waterborne polyurethane | |
| CN117843885B (en) | Organosilicon handfeel aid and preparation method and application thereof | |
| CN118325025A (en) | One-pot method for preparing polyurethane modified organosilicon softener | |
| CN116239778B (en) | A softening finishing agent capable of improving soap-resistant performance of fabric | |
| CN114134717B (en) | Preparation method of fabric handfeel agent | |
| CN112962314B (en) | Multi-arm associated polyurethane composite modified organic silicon softener emulsion and preparation method thereof |
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 |