CN115322385B - Multi-branched multifunctional emulsifier and preparation method and application thereof - Google Patents
Multi-branched multifunctional emulsifier and preparation method and application thereof Download PDFInfo
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- CN115322385B CN115322385B CN202211077985.9A CN202211077985A CN115322385B CN 115322385 B CN115322385 B CN 115322385B CN 202211077985 A CN202211077985 A CN 202211077985A CN 115322385 B CN115322385 B CN 115322385B
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- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 59
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 239000000835 fiber Substances 0.000 claims abstract description 43
- 229920000728 polyester Polymers 0.000 claims abstract description 43
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 16
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 10
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims description 23
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 16
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 6
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 claims description 6
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 tetraalkylammonium carboxylate Chemical class 0.000 description 4
- 206010020112 Hirsutism Diseases 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000007380 fibre production Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 239000008041 oiling agent Substances 0.000 description 2
- 239000008601 oleoresin Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- GGUPMVXPXHZNKF-UHFFFAOYSA-N benzene-1,2-diol;formaldehyde Chemical compound O=C.OC1=CC=CC=C1O GGUPMVXPXHZNKF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000002268 wool Anatomy 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D06M15/55—Epoxy resins
-
- 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
- D06M2200/35—Abrasion, pilling or fibrillation resistance
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)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Epoxy Resins (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The application provides a multi-branched multifunctional emulsifier, and a preparation method and application thereof, and belongs to the technical field of fiber preparation. The preparation method of the multi-branched multi-functional emulsifier comprises the steps of mixing and reacting anhydride and a viscous polymer containing hydroxyl groups to prepare polyester containing carboxylic acid, mixing and reacting polyester, epoxy resin and an initiator to enable a plurality of epoxy groups of the epoxy resin and carboxyl groups of the polyester to react to form a multi-branched structure, and preparing the multi-branched multi-functional emulsifier. The epoxy resin contains at least 3 epoxy groups. The preparation method of the emulsifier can prepare the emulsifier with multi-branched and multi-functional structure, the emulsifier has the characteristic of high compatibility, and the emulsifier has better emulsifying property for oily resin, especially for multi-functional epoxy resin, has better emulsifying property, good stability of an emulsifying product, and better film forming effect of the emulsifying product on fibers, and basically does not form particles or hollow areas on the surfaces of the fibers.
Description
Technical Field
The application relates to the technical field of fiber preparation, in particular to a multi-branched multifunctional emulsifier, a preparation method and application thereof.
Background
The aqueous oiling or sizing agent is indispensable in the fiber production and high-performance fiber preparation processes, and the emulsifier is a key core raw material of the aqueous oiling or sizing agent and has a crucial effect on the characteristics of stability, uniformity, wettability and the like of the high-quality oiling agent.
At present, the epoxy emulsion used for the water-based oiling agent or sizing agent for domestic fiber production mostly adopts difunctional epoxy resin, and has short performance plates with few functional groups, small molecular volume, low film forming strength and the like. The multifunctional epoxy emulsion is used for coating the fiber, so that a film forming substance with higher strength can be formed on the surface of the fiber, the fiber hairiness can be reduced, but the general emulsifier is difficult to emulsify the multifunctional epoxy resin with special structure, and the production requirements of high-quality fiber cannot be met due to the performance defects of low structural compatibility, poor emulsifying capacity and the like.
Disclosure of Invention
The application provides a multi-branched multifunctional emulsifier, a preparation method and application thereof, which have better emulsifying capacity and stability, and can be used for producing multifunctional epoxy emulsion so as to prepare high-quality fiber.
Embodiments of the present application are implemented as follows:
in a first aspect, the present examples provide a method of preparing a multi-branched multifunctional emulsifier comprising: the method comprises the steps of mixing and reacting anhydride and a viscous hydroxyl-containing polymer to obtain carboxylic acid-containing polyester, mixing and reacting polyester, epoxy resin and an initiator to enable a plurality of epoxy groups of the epoxy resin and carboxyl groups of the polyester to react to form a multi-branched structure, and obtaining the multi-branched multifunctional emulsifier.
The epoxy resin contains at least 3 epoxy groups.
In the technical scheme, the preparation method of the multi-branched multifunctional emulsifier can prepare the emulsifier with a multi-branched and multifunctional structure, the emulsifier has the characteristic of high compatibility, the emulsifier has good emulsifying property for oily resin, particularly for multifunctional epoxy resin, the emulsifying product has good stability, the film forming effect of the emulsifying product on fibers is good, and particles or hollow areas are not formed on the surfaces of the fibers basically.
With reference to the first aspect, in a first possible example of the first aspect of the present application, the amount ratio of the polymer and the acid anhydride is 1:0.8 to 1.2, and the amount ratio of the polymer and the epoxy resin is 1:1/3 to 1/4.
With reference to the first aspect, in a second possible example of the first aspect of the present application, the polymer includes polyethylene glycol monomethyl ether, polycaprolactone diol, or polyethylene glycol.
Alternatively, the molecular weight of the polymer is 1000 to 20000.
With reference to the first aspect, in a third possible example of the first aspect of the present application, the above-mentioned hydroxyl group-containing polymer in a viscous state is produced by:
heating the polymer to 110-180 ℃ under the protection of inert gas until the polymer is converted into a viscous state.
In the above examples, the polymer is warmed to 110℃to 180℃and the polymer reaches a viscous flow temperature, causing the polymer to change to a viscous flow state.
With reference to the first aspect, in a fourth possible example of the first aspect of the present application, the above-mentioned acid anhydride includes maleic anhydride, phthalic anhydride, or nadic anhydride.
In a fifth possible example of the first aspect of the present application, in combination with the first aspect, the hydroxyl group-containing polymer in the viscous state described above and the acid anhydride are mixed and reacted at 110 to 180℃for 2 to 6 hours to produce the carboxylic acid-containing polyester.
In the above examples, the anhydride is ring opened to form two carboxylic acids, the anhydride being reacted with one of the hydroxyl groups of the polymer by one of the carboxylic acids, such that the hydroxyl-containing polymer and the anhydride react to form the carboxylic acid-containing polyester.
With reference to the first aspect, in a sixth possible example of the first aspect of the present application, the epoxy resin includes a tetraphenolethane tetraglycidyl ether epoxy resin, a resorcinol formaldehyde tetraglycidyl ether epoxy resin, or a diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate epoxy resin.
With reference to the first aspect, in a seventh possible example of the first aspect of the present application, the above polyester, epoxy resin and initiator are mixed and reacted at 110 to 180 ℃ for 3 to 8 hours to prepare the multi-branched multifunctional emulsifier.
In the above examples, the carboxyl groups of the plurality of polyesters are respectively reacted with different epoxy groups of the epoxy resin, thereby allowing the plurality of polyesters to be attached to the epoxy resin, forming an emulsifier having a multi-branched, multi-functional structure.
In a second aspect, the present example provides a multi-branched multifunctional emulsifier prepared according to the above-described method of preparing a multi-branched multifunctional emulsifier.
In the technical scheme, the emulsifier provided by the application has the characteristics of multi-branching and multi-functional group structure and high compatibility, has good emulsifying property for oily resin, particularly has good emulsifying property for multi-functional group epoxy resin, has good stability of an emulsifying product, has good film forming effect of the emulsifying product on fibers, and basically does not form particles or hollow areas on the surfaces of the fibers.
In a third aspect, the present application exemplifies the provision of a multi-branched multifunctional emulsifier prepared according to the above-described preparation method of a multi-branched multifunctional emulsifier or the use of the above-described multi-branched multifunctional emulsifier in the preparation of fibers.
In the above technical scheme, the multi-branched multifunctional emulsifier of the present application can be used for producing high quality fibers.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a reaction scheme of example 1 of the present application;
FIG. 2 is a reaction scheme of example 2 of the present application;
FIG. 3 is a reaction scheme of example 3 of the present application;
FIG. 4 is a reaction scheme of comparative example 3 of the present application;
FIG. 5 is a reaction scheme of comparative example 4 of the present application.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The inventor finds that the emulsion product obtained by emulsifying the oleoresin by adopting the existing emulsifying agent has poor film forming effect on the fiber, particles are easy to form on the surface of the fiber, and some areas of the surface of the fiber are not covered with the film forming agent to form hole areas, the hole areas are easy to fuzze, and the interface bonding ratio of the fiber and other materials is poor when the fiber forms the fiber composite material with other materials, so that the obtained fiber composite material has more internal defects.
The following is a specific description of a multi-branched multifunctional emulsifier, a preparation method and application thereof according to the embodiment of the present application:
the application provides a preparation method of a multi-branched multifunctional emulsifier, which comprises the following steps:
s1, preparing a viscous hydroxyl polymer
Adding polymer containing hydroxyl into a container, continuously introducing protective gas, then heating to 110-180 ℃ until the polymer containing hydroxyl is melted, stirring uniformly, and converting the polymer into viscous state.
The polymer comprises polyethylene glycol monomethyl ether, polycaprolactone diol, or polyethylene glycol.
As an example, the polymer may be polyethylene glycol monomethyl ether, or may be polycaprolactone diol, or may be polyethylene glycol.
Alternatively, the molecular weight of the polymer is 1000 to 20000.
As examples, the molecular weight of the polymer may be 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, or 20000.
The shielding gas includes helium, neon, xenon or nitrogen.
As an example, the shielding gas may be helium, neon, xenon or nitrogen.
As an example, the temperature may be raised to 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃ to convert the polymer into a viscous state.
S2, preparing carboxyl-containing polyester
The acid anhydride and the viscous polymer containing hydroxyl are mixed and reacted at 110-180 deg.c for 2-6 hr to obtain the polyester containing carboxylic acid.
The acid anhydride is opened to form two carboxylic acids, the acid anhydride reacts with one hydroxyl group of the polymer through one carboxylic acid, so that the hydroxyl-containing polymer and the acid anhydride react to form the carboxylic acid-containing polyester, and the other hydroxyl group of the polymer can enable the emulsifier to have better water solubility.
The mass ratio of the polymer to the anhydride is 1:0.8-1.2.
As examples, the mass ratio of polymer to anhydride may be 1:0.8, 1:0.9, 1:1, 1:1.1, or 1:1.2.
The acid anhydride includes maleic anhydride, phthalic anhydride or nadic anhydride.
By way of example, the anhydride may be maleic anhydride, or may be phthalic anhydride, or may be nadic anhydride.
As an example, the carboxylic acid-containing polyester may be prepared by reacting at 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃ for 2 hours, 3 hours, 4 hours, 5 hours or 6 hours.
S3, preparing multi-branched multifunctional emulsifier
The polyester, the epoxy resin and the initiator are mixed and react for 3 to 8 hours at the temperature of between 110 and 180 ℃ to prepare the multi-branched multifunctional emulsifier.
The carboxyl groups of the plurality of polyesters react with different epoxy groups of the epoxy resin, respectively, so that the plurality of polyesters are connected to the epoxy resin to form the emulsifier with a multi-branched and multi-functional structure.
The mass ratio of the polymer to the epoxy resin is 1:1/3-1/4.
As an example, the mass ratio of polymer to epoxy resin may be 1:1/3 or 1:1/4.
The mass fraction of the initiator in the system is 0.2-0.7 wt%.
As an example, the mass fraction of initiator in the system may be 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt% or 0.7wt%.
Optionally, the epoxy resin contains at least 3 epoxy groups.
Alternatively, the epoxy resin contains 3 to 4 epoxy groups.
The epoxy resin includes tetraphenolethane tetraglycidyl ether epoxy resin, resorcinol formaldehyde tetraglycidyl ether epoxy resin or 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester epoxy resin.
As an example, the epoxy resin may be a tetraphenolethane tetraglycidyl ether epoxy resin, or may be a benzenediol formaldehyde tetraglycidyl ether epoxy resin, or may be a 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester epoxy resin.
The initiator comprises tetrabutylammonium bromide, ammonium persulfate or tetraalkylammonium carboxylate.
As an example, the initiator may be tetrabutylammonium bromide, or may be ammonium persulfate, or may be tetraalkylammonium carboxylate.
As an example, the multi-branched multifunctional emulsifier may be prepared by reacting at 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃ for 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours.
The preparation method of the multi-branched multi-functional emulsifier can prepare the emulsifier with a multi-branched and multi-functional structure, the emulsifier has the characteristic of high compatibility, and the emulsifier has better emulsifying property for oily resin, particularly for multi-functional epoxy resin, has better emulsifying property, good stability of an emulsifying product, and better film forming effect of the emulsifying product on fibers, and basically does not form particles or hollow areas on the surfaces of the fibers.
The application also provides a multi-branched multi-functional emulsifier which is prepared according to the preparation method of the multi-branched multi-functional emulsifier.
The emulsifier provided by the application has a multi-branched and multi-functional structure, has the characteristic of high compatibility, has good emulsifying property on oily resin, and particularly has good emulsifying property on multi-functional epoxy resin, good stability of an emulsified product, good film forming effect of the emulsified product on fibers, and basically no particulate matters or hollow areas are formed on the surfaces of the fibers.
The application also provides a multi-branched multifunctional emulsifier prepared by the preparation method of the multi-branched multifunctional emulsifier or application of the multi-branched multifunctional emulsifier in preparing fibers.
The multi-branched multifunctional emulsifier is used for preparing an emulsified product with the oleoresin, and the emulsified product is used for coating the surface of the fiber to form a protective layer, so that the high-quality fiber is obtained.
Oily solvents include various epoxy resins.
A multi-branched multifunctional emulsifier and a method for preparing the same according to the present application are described in further detail below with reference to examples.
Example 1
The embodiment of the application provides a multi-branched multifunctional emulsifier and a preparation method thereof, wherein the multi-branched multifunctional emulsifier comprises the following steps:
s1, preparing a viscous polymer containing hydroxyl
Adding polyethylene glycol monomethyl ether CH with molecular weight of 1000 into a container 3 (OC 2 H 4 ) n -OH, continuously introducing nitrogen, then heating to 110 ℃ until polyethylene glycol monomethyl ether is converted into a viscous state, and uniformly stirring.
S2, preparing carboxyl-containing polyester
Phthalic anhydride and viscous statePolyethylene glycol monomethyl ether of (A) and reacting at 110 ℃ for 6 hours to obtain polyester CH containing carboxylic acid 3 (OC 2 H 4 ) n OOCR 1 -COOH。
The mass ratio of phthalic anhydride to viscous polyethylene glycol monomethyl ether is 1:1.
S3, preparing multi-branched multifunctional emulsifier
The prepared polyester containing carboxylic acid, tetraphenolethane tetraglycidyl ether epoxy resin and tetrabutylammonium bromide are mixed and reacted for 8 hours at the temperature of 110 ℃ to prepare the multi-branched multifunctional emulsifier (CH 3 (OC 2 H 4 ) n OOCR 1 -COOCH 2 (OH)CH) 4 R。
The mass ratio of the carboxylic acid-containing polyester to the tetraphenolethane tetraglycidyl ether epoxy resin was 1:1/4.
The mass fraction of tetrabutylammonium bromide in the system was 0.7wt%.
A reaction scheme of example 1 of the present application is shown in FIG. 1.
Example 2
The embodiment of the application provides a multi-branched multifunctional emulsifier and a preparation method thereof, wherein the multi-branched multifunctional emulsifier comprises the following steps:
s1, preparing a viscous polymer containing hydroxyl
Adding polycaprolactone diol HOCH with molecular weight of 3000 into a container 2 -(OC 5 H 10 CO) m OR 1 O(OCC 5 H 10 O) n -CH 2 OH, continuously introducing nitrogen, then heating to 180 ℃ until the polycaprolactone diol is converted into a viscous state, and uniformly stirring.
S2, preparing carboxyl-containing polyester
Mixing maleic anhydride and viscous polycaprolactone diol, and reacting at 180deg.C for 2 hr to obtain polyester HOCH containing carboxylic acid 2 -(OC 5 H 10 CO) m OR 1 O(OCC 5 H 10 O) n -CH 2 OOCR 2 -COOH。
The mass ratio of maleic anhydride to the viscous polycaprolactone diol was 1:1.
S3, preparing multi-branched multifunctional emulsifier
The prepared polyester containing carboxylic acid, resorcinol formaldehyde tetraglycidyl ether epoxy resin and ammonium persulfate are mixed and reacted for 3 hours at 180 ℃ to prepare the multi-branched multifunctional emulsifier (HOCH 2 -(OC 5 H 10 CO) m OR 1 O(OCC 5 H 10 O) n -CH 2 OOCR 2 -COOCH 2 (OH)CH) 4 R。
The mass ratio of the carboxylic acid-containing polyester to the resorcinol formaldehyde tetraglycidyl ether epoxy resin was 1:1/4.
The mass fraction of ammonium persulfate in the system is 0.2wt%.
A reaction scheme of example 2 of the present application is shown in FIG. 2.
Example 3
The embodiment of the application provides a multi-branched multifunctional emulsifier and a preparation method thereof, wherein the multi-branched multifunctional emulsifier comprises the following steps:
s1, preparing a viscous polymer containing hydroxyl
Adding polyethylene glycol HOCH with molecular weight of 10000 into container 2 -(OC 2 H 4 ) n -OH, continuously introducing nitrogen, then heating to 140 ℃, converting polyethylene glycol into viscous state, and uniformly stirring.
S2, preparing carboxyl-containing polyester
Mixing nadic anhydride and viscous polyethylene glycol, and reacting at 140 deg.C for 4 hr to obtain polyester HOCH containing carboxylic acid 2 -(OC 2 H 4 ) n OOCR 1 -COOH。
The mass ratio of the nadic anhydride to the viscous polyethylene glycol is 1:1.
S3, preparing multi-branched multifunctional emulsifier
The prepared polyester containing carboxylic acid, 4, 5-epoxycyclohexane-1, 2-diglycidyl ester epoxy resin and tetraalkylammonium carboxylate are mixed and reacted for 5 hours at 140 ℃ to prepare the multi-branched multifunctional emulsifier (HOCH 2 -(OC 2 H 4 ) n OOCR 1 -COOCH 2 (OH)CH) 3 R。
The mass ratio of the carboxylic acid-containing polyester to the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester epoxy resin was 1:1/4.
The mass fraction of the tetraalkylammonium carboxylate in the system was 0.5wt%.
A reaction scheme of example 3 of the present application is shown in FIG. 3.
Comparative example 1
An aqueous epoxy emulsifier, shenyang, is a manufacturer.
Comparative example 2
An aqueous epoxy emulsifier, jining, is a manufacturer.
Comparative example 3
The application provides an emulsifier and a preparation method thereof, wherein the emulsifier comprises the following steps:
s1, preparing a viscous polymer containing hydroxyl
Adding polyethylene glycol monomethyl ether CH with molecular weight of 1000 into a container 3 (OC 2 H 4 ) n -OH, continuously introducing nitrogen, then heating to 110 ℃ until polyethylene glycol monomethyl ether is converted into a viscous state, and uniformly stirring.
S2, preparing carboxyl-containing polyester
Mixing phthalic anhydride and viscous polyethylene glycol monomethyl ether, and reacting at 110deg.C for 6 hr to obtain polyester CH containing carboxylic acid 3 (OC 2 H 4 ) n OOCR 1 -COOH。
The mass ratio of phthalic anhydride to viscous polyethylene glycol monomethyl ether is 1:1.
S3, preparing an emulsifier
The resulting carboxylic acid-containing polyester, epoxy resin E51 and tetrabutylammonium bromide were mixed and reacted at 110℃for 8 hours to prepare an emulsifier (CH) 3 (OC 2 H 4 ) n OOCR 1 -COOCH 2 (OH)CH) 2 R。
The mass ratio of the carboxylic acid-containing polyester to the epoxy resin E51 was 1:1/2.
A reaction scheme of comparative example 3 of the present application is shown in FIG. 4.
Comparative example 4
The application provides an emulsifier and a preparation method thereof, wherein the emulsifier comprises the following steps:
s1, preparing a viscous polymer containing hydroxyl
Adding polyethylene glycol monomethyl ether CH with molecular weight of 1000 into a container 3 (OC 2 H 4 ) n -OH, continuously introducing nitrogen, then heating to 110 ℃ until polyethylene glycol monomethyl ether is converted into a viscous state, and uniformly stirring.
S2, preparing carboxyl-containing polyester
Mixing phthalic anhydride and viscous polyethylene glycol monomethyl ether, and reacting at 110deg.C for 6 hr to obtain polyester CH containing carboxylic acid 3 (OC 2 H 4 ) n OOCR 1 -COOH。
The mass ratio of phthalic anhydride to viscous polyethylene glycol monomethyl ether is 1:1.
S3, preparing an emulsifier
The prepared polyester containing carboxylic acid, butyl glycidyl ether and tetrabutylammonium bromide are mixed and reacted for 8 hours at the temperature of 110 ℃ to prepare the emulsifier CH 3 (OC 2 H 4 ) n OOCR 1 -COOCH 2 (OH)CHR。
The mass ratio of the carboxylic acid-containing polyester to the butyl glycidyl ether was 1:1/2.
A reaction scheme of comparative example 4 of the present application is shown in FIG. 5.
Test example 1
The emulsifiers prepared in examples 1 to 3 and comparative examples 1 to 4 were respectively taken, the prepared emulsifiers and the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester epoxy resin were mixed to prepare emulsified products, the particle diameters of the emulsified products were detected, and the emulsified products were centrifuged at 2500r/min for 30min by using a centrifuge, and whether the emulsified products were layered or not was observed, and the detection results are shown in table 1.
TABLE 1 stability of the emulsion products obtained according to the emulsifier configurations of examples 1 to 3 and comparative examples 1 to 4
| Project | Particle size | Layering situation |
| Example 1 | ≤350nm | Non-layering |
| Example 2 | ≤350nm | Non-layering |
| Example 3 | ≤250nm | Non-layering |
| Comparative example 1 | ≤1500nm | Layering |
| Comparative example 2 | ≤1500nm | Layering |
| Comparative example 3 | ≤500nm | Slightly layered |
| Comparative example 4 | ≤500nm | Layering |
As can be seen from the comparison of examples 1 to 3 and comparative examples 1 to 2, the multi-branched multifunctional emulsifier of the embodiment of the application has good stability of the emulsified product, and has good emulsification effect on trifunctional epoxy resin, which is superior to the common epoxy emulsifier in the market.
As is clear from the comparison of example 1 and comparative examples 3 to 4, the multi-branched multifunctional emulsifier of example 1 of the present application has a larger number of functional groups than the emulsifiers of comparative examples 3 to 4, and the multi-branched multifunctional emulsifier of example 1 has a higher emulsifying ability for the multifunctional epoxy resin than the emulsifiers of comparative examples 3 to 4.
Test example 2
Each emulsified product prepared in test example 1 was coated on the surface of a fiber, dried to form a film, and the amount of the filaments of the fiber was measured, and the abrasion resistance of the emulsified product after film formation was measured, and the detection results are shown in table 2.
The method for testing the fiber hairiness comprises the following steps: after passing through 3 rods, the fiber tows are clamped by two sponges (32 mm is 64mm is 10 mm), a certain pressure is applied to enable the distance between the sponges to be 5mm, the fiber traction speed is 15m/min, the running time is 20min, and the quantity (g) of the wool attached to the sponges is measured.
TABLE 2 test example 1 each emulsified product was coated on the surface of a fiber, dried to form a film, and the amount of hairiness of the fiber was measured
| Project | Quantity of broken filaments (mg) |
| Example 1 | 45～55 |
| Example 2 | 45～55 |
| Example 3 | 30～40 |
| Comparative example 1 | 115～125 |
| Comparative example 2 | 85～95 |
| Comparative example 3 | 75～85 |
| Comparative example 4 | 90～100 |
As is clear from comparison of examples 1 to 3 and comparative examples 1 to 2, the emulsified product prepared from the multi-branched multifunctional emulsifier of the embodiment of the application is coated on the surface of the fiber, and the amount of the filaments of the fiber is small after the fiber is dried to form a film; the emulsified product prepared by the common epoxy emulsifier in the market is coated on the surface of the fiber, and after the fiber is dried to form a film, the quantity of the filaments of the fiber is more. Namely, the multi-branched multifunctional emulsifier provided by the embodiment of the application has good emulsification effect on the trifunctional epoxy resin, and the wear resistance of the film forming material is superior to that of the common epoxy emulsifier in the market.
As is clear from the comparison of example 1 and comparative examples 3 to 4, the multi-branched multifunctional emulsifier of example 1 of the present application has a larger number of functional groups than the emulsifiers of comparative examples 3 to 4, and the higher the emulsifying ability of the multifunctional epoxy resin, the better the abrasion resistance of the film forming material.
The above description is only of specific embodiments of the application and is not intended to limit the application, but various modifications and variations can be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (7)
1. A method for preparing a multi-branched multi-functional emulsifier, characterized in that the method for preparing the multi-branched multi-functional emulsifier comprises: mixing and reacting anhydride and a viscous hydroxyl-containing polymer to obtain carboxylic acid-containing polyester, and mixing and reacting the polyester, epoxy resin and an initiator to enable a plurality of epoxy groups of the epoxy resin and carboxyl groups of the polyester to react to form a multi-branched structure, so as to obtain the multi-branched multifunctional emulsifier;
the epoxy resin contains at least 3 epoxy groups;
the mass ratio of the polymer to the anhydride is 1:0.8-1.2, and the mass ratio of the polymer to the epoxy resin is 1:1/3-1/4;
the polymer comprises polyethylene glycol monomethyl ether, polycaprolactone diol or polyethylene glycol;
the acid anhydride comprises maleic anhydride, phthalic anhydride or nadic anhydride;
the epoxy resin comprises tetraphenolethane tetraglycidyl ether epoxy resin, resorcinol formaldehyde tetraglycidyl ether epoxy resin or 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester epoxy resin.
2. The method for producing a multi-branched polyfunctional emulsifier according to claim 1, wherein said polymer has a molecular weight of 1000 to 20000.
3. The method for producing a multi-branched polyfunctional emulsifier according to claim 1, wherein said viscous flow-state hydroxyl-containing polymer is produced by:
and heating the polymer to 110-180 ℃ under the protection of inert gas until the polymer is converted into a viscous state.
4. The method for producing a multi-branched polyfunctional emulsifier according to claim 1, wherein said hydroxyl group-containing polymer in a viscous state and said acid anhydride are mixed and reacted at 110 to 180 ℃ for 2 to 6 hours to produce said carboxylic acid-containing polyester.
5. The method for preparing the multi-branched multi-functional emulsifier according to claim 1, wherein the polyester, the epoxy resin and the initiator are mixed and reacted at 110 ℃ to 180 ℃ for 3 hours to 8 hours to prepare the multi-branched multi-functional emulsifier.
6. A multi-branched multi-functional emulsifier characterized in that the multi-branched multi-functional emulsifier is produced according to the production method of the multi-branched multi-functional emulsifier according to any one of claims 1 to 5.
7. Use of the multi-branched multifunctional emulsifier produced by the production method of the multi-branched multifunctional emulsifier according to any one of claims 1 to 5 or the multi-branched multifunctional emulsifier according to claim 6 for producing fibers.
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