CN109400882B - A kind of ammonia hydrosiloxane polymer and preparation method thereof - Google Patents
A kind of ammonia hydrosiloxane polymer and preparation method thereof Download PDFInfo
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- CN109400882B CN109400882B CN201811270901.7A CN201811270901A CN109400882B CN 109400882 B CN109400882 B CN 109400882B CN 201811270901 A CN201811270901 A CN 201811270901A CN 109400882 B CN109400882 B CN 109400882B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000004753 textile Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 11
- -1 polyoxy Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000002170 ethers Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 239000004530 micro-emulsion Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 125000000373 fatty alcohol group Chemical group 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 230000010148 water-pollination Effects 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 4
- 239000010985 leather Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 15
- 238000012360 testing method Methods 0.000 description 9
- 239000004744 fabric Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229920013822 aminosilicone Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000007592 spray painting technique Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- 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
- D06M15/53—Polyethers
-
- 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
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention relates to polymeric material fields, in particular to a kind of ammonia hydrosiloxane polymer and preparation method thereof, specially polymer shown in formula (1), the polymer has good hydrophily, wearability, gas permeability, suitable for leather industry as softener or textile industry as suitable soft dose of the use of allotment
Description
Technical field
The invention belongs to high-molecular compound technical fields.More particularly to a kind of leading in leather containing organic siloxane polymer
The preparation and application in domain or light industry field of weaving.
Background technique
Textile product, which generally requires, takes necessary anti-corrosion, wear-resisting, submissive means to make the quality-improving of product, using softness
Agent protection is a kind of most simple and effective method.When protect and is submissive to fabric at present, usually used aqueous solution,
Other than aqueous solution, polysiloxanes can also be added, the shape of aqueous emulsion is usually temporarily configured to by means of suitable emulsifier
Formula.During industrial application, the application of the polysiloxanes of aqueous solution can lead to the problem of it is various, the reason is that making in Spray-painting machine
Used time, the high shear force of Spray-painting machine usually make creaming of emulsion, form siloxanes spot, pollute textile fabric, increase subsequent cleaning at
Sheet and difficulty.
At present using amino-alkyl silicane, hydroxyl polysiloxane as raw material, the amino for being widely used in various textile finishings can be made into
Polysiloxanes increases the tear resistance of textile fabric or leatherware, waterproof, prevents although can improve the appearance and flexibility of fabric or leatherware
Oil, more reflecting feel etc. ([J] insulating materials, 2006,39 (1): 59-63.), but traditional amino silicones wearability compared with
Difference, however it remains hydrophily is poor, so that the disadvantages of textile fabric gas permeability is deteriorated.
The present invention is intended to provide a kind of better amino silicones, reduce the arrangement cost of textile, increase textile
Wearability reduces textile processing difficulty and pollution.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new siloxane polymers and preparation method thereof, have more
Good hydrophily, wearability and gas permeability has better industrial application value.
Technical scheme is as follows:
The present invention provides a kind of ammonia hydrosiloxane polymer, the structure with polymer shown in formula (1):
Wherein, n is selected from 50~60, m and is selected from 40~80；
Work as R1And R2It is respectively and independently selected from unsubstituted-CH2When, x is selected from 1~5 arbitrary integer, and y is selected from 1~5 times
Meaning integer；
Or
Work as R1And R2It is respectively and independently selected from-the CH replaced by halogen, amino, a hydroxyl substituent2When, x and y are 1.
In preferred embodiment of the invention scheme, the halogen is selected from fluorine, chlorine, bromine, iodine.
In the preferred example scheme of the present invention, compound shown in formula (1) is selected from:
Further preferably
The present invention furthermore provides the synthetic method of polymer shown in above-mentioned formula (1), and synthetic route includes:
Wherein, n is selected from 50~60, m and is selected from 40~80；
Work as R1And R2It is respectively and independently selected from unsubstituted-CH2When, x is selected from 1~5 arbitrary integer, and y is selected from 1~5 times
Meaning integer；
Or
Work as R1And R2It is respectively and independently selected from-the CH replaced by halogen, amino, a hydroxyl substituent2When, x and y are 1.
In preferred embodiment of the invention scheme, the halogen is selected from fluorine, chlorine, bromine, iodine.
In the further preferred example scheme of the present invention, the specific synthesis step of polymer shown in formula (1) includes:
1, it is dissolved in organic solvent with compound (a) for starting material；
2, it in the presence of lewis acid (Lewis acid), is added compound (b), is heated to reflux, react 1-5 hours；
3, reaction product is filtered, separates organic phase, then by organic phase respectively with pure water, saturated sodium-chloride washing, with anhydrous
Sodium sulphate is dry；
4, it is spin-dried for solvent, obtains polymer shown in formula (1).
In the further preferred example scheme of the present invention, the organic solvent is selected from ethers, ketone, halogenated hydrocarbon, nitrile
Class.
In the preferred example scheme of the present invention, the ethers is selected from methyl tertiary butyl ether(MTBE), ether, tetrahydrofuran, two
Isopropyl ether and 1,4- dioxane；
The ketone is selected from acetone, 2- butanone, amyl- 2- ketone, amyl- 3- ketone, hex- 2- ketone and hex- 3- ketone；The halogenated hydrocarbon
Selected from methylene chloride and chloroform；The nitrile is selected from acetonitrile.
In the preferred example scheme of the present invention, the lewis acid is selected from LiClO4、ZnCl2、Ti(Oi-Pr)4。
In the preferred example scheme of the present invention, it is described be heated to reflux temperature be selected from 100~200 DEG C, preferably 120~
150℃。
The present invention also provides a kind of soft emulsions, include polymer, surfactant and water shown in formula (1).
The present invention furthermore provides the preparation method of the soft emulsion comprising polymer shown in above-mentioned formula (1), specific to close
Include at step:
1, polymer shown in a certain amount of formula (1) is taken, a small amount of surfactant stirs evenly；
2, add the sour agent tune pH to 6-7 of 30~50% (w/w)；
3, mixture is stirred, until there are a large amount of foams, a certain amount of water is slowly added to and stirs simultaneously, be prepared and contain
The microemulsion of polymer shown in formula (1).
In the further preferred example scheme of the present invention, the surfactant is anionic and non-ionic surface
The mixture of activating agent, the anionic surfactant is selected from fatty alcohol polyoxyethylene ether (such as AE09, AE020), described
Nonionic surface active agent is selected from esters polyvinyl chloride ethers (such as SG-12, SG-40), fatty alcohol polyoxypropylene ether class (SPO-
5、SPO-10、SPO-20)。
In the preferred example scheme of the present invention, the anionic surfactant and nonionic surface active agent
In mixture, the mass ratio of anionic surfactant and honionic surfactant mixture is 1:1~1:5, preferably
1:2、1:3。
In the preferred example scheme of the present invention, the anionic surfactant and nonionic surface active agent
There are two types of different HLB values for tool.
In the preferred example scheme of the present invention, HLB value is selected from 5~10.
In the preferred example scheme of the present invention, the acid agent is selected from acetic acid, sulfuric acid, hydrochloric acid or formic acid.
The present invention still further provides the application side of the soft emulsion comprising polymer shown in formula (1) on the textile
Method, the method are selected from padding process and impregnation technology.
Detailed description of the invention
Advantageous effect of the invention
Compared with prior art, technical solution of the present invention has the advantage that
The siloxane polymer that the present invention is prepared overcomes the lance between the hydrophily of hydrophilic silicon oil and flexibility
Shield is keeping hydrophilic while hydrophilic silicon oil in advance wearability, flexibility, gas permeability, and is not polluting fabric, is suitable for
Caused by spinning industrial production.
Specific embodiment
The preparation of embodiment 1, compound (a1)
Reagent: compound (a1) is purchased from Shen Yao (Xianghe) Science and Technology Ltd.；Compound (b1) is referring to patent
The preparation of US3971627A the method；LiClO4It buys from Shanghai China Lithium Industrial Co., Ltd..
Synthetic route is as follows:
Specific preparation method:
Compound (a1) 90g is dissolved in the THF (tetrahydrofuran) of the warm of 250mL, 1g LiClO is added4And compound
(b1), under nitrogen protection, control temperature is about 150~200 DEG C, is heated to reflux, and is reacted 3 hours.After reaction, it will mix
Object filtering, isolates organic phase.Gained organic phase is successively washed with pure water, saturated sodium-chloride, then dry with anhydrous sodium sulfate,
Finally it is spin-dried for obtaining compound (1a).The modified polyorganosiloxane is about 350000mPa.S in 25 DEG C of viscosity, and molecular weight is about
170500, the degree of polymerization 1656.
According to infrared spectrogram:
1057.6cm-1Show containing Si-O；1010.5cm-1Show containing Si-C；1257.8cm-1、786.3cm-1Show to contain
There is Si-CH3, Si- (CH3)3Structure；2959cm-1Show containing methyl structural, 3650~3580cm-1Place shows containing hydroxyl knot
Structure；3500~3300cm-1Show containing secondary amine structure；3100~3000cm-1And 1500~1600cm-1Show containing substituted benzene
Base.
According to nmr spectrum1H-NMR:
δ=0.07 is Si-CH3Middle H absorption peak；δ=0.61 is Si-CH2The absorption peak of middle H；δ=1.31 are-CH2Middle H
Absorption peak (remove the directly-CH that is connected with Si2-)。
Embodiment 2, the preparation containing compound (a1) soft emulsion.
By the fatty alcohol polyoxyethylene ether AE09 and esters polyvinyl chloride ethers SG-40 of 20g compound (a1) and 3mL (1:
2, w/w) compound mixing stirs evenly, and 4mL hydrochloric acid is then added, continues to stir evenly, makes pH range 6~7；Continue to stir compound
Until there are a large amount of foams, it is then slow added into 100mL water, is stirred simultaneously, the microemulsion of (1a) compound is contained.
Embodiment 3, mechanical stability test
Sample: comparative example is prepared referring to 3 the method for patent CN10148518A embodiment；Test example sample according to
The preparation of 2 the method for embodiment.
Test method: be about weighed into the appropriate vessel of 500mL (diameter about 100mm, height about 180mm) (400 ±
0.5) g has filtered the lotion of (aperture is 177 μm, the strainer of 80 mesh), places it on high speed dispersion base, is fixed with clip,
Dispersing agent (stirring-head is fluted disc type, diameter about 40mm) is started, adjusts the speed as 2500r/min, disperses 0.5h, refilter, and with certainly
Water rushes the residue on container inner wall into strainer, and with tap water flushing filtering net, dry all sediments calculate sediment
Mass percent, above-mentioned experiment is measured in parallel 3 times；Whether lotion is demulsified in observation dispersion process and whether there is or not apparent flocculations
Object.
The mechanically stable Journal of Sex Research of 1 lotion of table
| Sample | Comparative example | Test example sample |
| Percentage sediment | 17% | 6%** |
| Whether apparent flocculate is had | Have | Nothing |
Statistical method uses " T-test ", and * * indicates P < 0.01.
Experimental result: the mechanical stability of test example sample is substantially better than comparative example.
Embodiment 4, abrasion test
Sample: referring to embodiment 3.
Test method: according to the method for ASTM1044, emery wheel CS-10F is packed into Tai Boer abrasion testing device, in 500g
Applied load under make 500 turns of sample rotates to be assessed, the mist degree of sample before and after contrast test, and find out haze change (Δ H),
Evaluate wearability based on following standard: Δ H≤5.0, wearability are good；5.0 < Δ H < 10.0, wear no resistance；10.0≤Δ H,
Wearability is very poor.
Test result: Δ H≤5.0 of test example sample, wearability are good；And comparative example 10.0≤Δ H, wearability
It is very poor.
In summary, a kind of ammonia hydrosiloxane polymer of the present invention is compared with traditional siloxane polymer,
It is significantly increased in hydrophily, wearability, is more advantageous to the production of weaving light industry.
Claims (8)
1. a kind of ammonia hydrosiloxane polymer, which is characterized in that the structure with polymer shown in formula as follows (1):
Wherein, n is selected from 50~60, m and is selected from 40~80；
Work as R1And R2It is respectively and independently selected from unsubstituted-CH2When, x be selected from 1~5 arbitrary integer, y be selected from 1~5 it is any whole
Number；
Or
Work as R1And R2It is respectively and independently selected from-the CH replaced by halogen, amino, a hydroxyl substituent2When, x and y are 1.
2. ammonia hydrosiloxane polymer as described in claim 1, which is characterized in that the halogen is selected from fluorine, chlorine, bromine, iodine.
3. such as the described in any item ammonia hydrosiloxane polymer of claim 1~2, which is characterized in that gather shown in the formula (1)
Object is closed to be selected from:
4. a kind of softness emulsion, which is characterized in that include polymer as claimed in any one of claims 1 to 3, surfactant
And water.
5. a kind of method for preparing soft emulsion as claimed in claim 4, comprises the following steps:
(1) polymer shown in modus ponens (1), surfactant stir evenly；
(2) add the sour agent tune pH to 6-7 of 30~50% (w/w)；
(3) mixture is stirred, until there are a large amount of foams, a certain amount of water is slowly added to and stirs simultaneously, be prepared containing formula
(1) microemulsion of polymer shown in.
6. the method as claimed in claim 5 for preparing soft emulsion, which is characterized in that the surfactant is anionic
The mixture of surfactant and nonionic surface active agent；The anionic surfactant is selected from fatty alcohol polyoxy second
Alkene ether；The nonionic surface active agent is selected from esters polyvinyl chloride ethers or fatty alcohol polyoxypropylene ether class；The acid agent
Selected from acetic acid, sulfuric acid, hydrochloric acid or formic acid.
7. the method as claimed in claim 6 for preparing soft emulsion, which is characterized in that in the mixture, anionic table
The mass ratio of face activating agent and nonionic surface active agent is selected from 1:1~1:5.
8. a kind of application method of soft emulsion comprising polymer as claimed in any one of claims 1 to 3 on the textile,
It is characterized in that, the method is selected from padding process and impregnation technology.
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