CN105694046A - Preparation method of highly-branched block polyether-aminosiloxane finishing agent - Google Patents
Preparation method of highly-branched block polyether-aminosiloxane finishing agent Download PDFInfo
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- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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- 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
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
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- D—TEXTILES; PAPER
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
A preparation method of a highly-branched block polyether-aminosiloxane finishing agent includes the steps of firstly, enabling linear dimethyl hydrosilane-terminated dimethylsiloxane and oligomeric hydrogen-containing (sesqui) siloxane containing multiple Si-H bonds to undergo hydrosilation addition reaction with an allyl epoxy compound, and synthesizing an intermediate, namely epoxy group-modified polydimethylsiloxane/oligomeric (sesqui) siloxane blend; then, subjecting the intermediate and polyether amine to aminolysis ring-opening reaction in an organic solvent so as to synthesize the highly-branched block polyether-aminosiloxane finishing agent.When being used for finishing fiber fabrics after softening, the highly-branched block polyether-aminosiloxane finishing agent is capable of improving softness and hand feel of the fabrics remarkably and endowing the fabrics with high elasticity and excellent stiffness, moisture-absorbing and anti-static performance.
Description
Technical field
The invention belongs to textile finshing agent technical field, particularly to the preparation method of a kind of highly branched block polyether amino silicone finishing agent。
Background technology
Block polyether amino silicone oil, that is molecular backbone structure is simultaneously embedded in the general name of a polysiloxanes of polyethers amino group and polysiloxane segment。Block polyether amino silicone oil, multiple advantage with polyether group, ammonia hydrocarbyl functional group and polysiloxane, Final finishing for fabric, the soft comfortable of fabric, smooth feel or fluffy fine and smooth feel can be given, the performance such as fabric moisture, antistatic can be improved again, thus become the class functional after-finishing auxiliary agent that textile finshing agent field is most popular。This puts visible document publication number respectively [CN104650364], [CN103215817], [CN104233821], [CN103497307], [CN104195836], [CN102964602] Chinese invention patent etc.。
At present, on weaving market, the block polyether amino silicone of production and sales is mainly the silicone product of straight chain or linear structure, if the structure making this linear polyether amino silicone occurs hyperbranched or highly branched, then can not only improve film property and the membrane structure of polyethers amino silicone, and be expected to make the softness of block polyether amino silicone and feel produce abundant change, the existing people of this respect has done certain exploration work。Such as CN104650364A utilizes diepoxy polyether-based tetramethyl siloxanes and D4First reaction forms α, the silicone oil intermediate of ω-epoxidized polyether end-blocking, then again this intermediate and diethylenetriamine are reacted synthesized by hyperbranched network structure polyethers amino silicone, it is said can not only cohesive force between fortifying fibre yarn, and can imparting process after the good flexibility of fabric and resilience。
Another compared with existing linearity block polyethers amino silicone, the block polyether amino silicone of hyperbranched or highly branched (abbreviation highly-branched), not only have performance and the feature of linear amino silicone, and flexible smooth and the hands sense of similar linear macromolecule block polyether amino silicone can be obtained compared with low-viscosity or less mean molecule quantity when, but elasticity more preferably and is more easy to emulsifying, but how to utilize prior art to carry out synthesis of super branched or highly branched, the novel polyether amino silicone of resin-like/network structure and easily industrialized production, it is not only the problem that synthesis aspect is badly in need of solving, and become and improve polyethers amino silicone application performance such as softness further, an elastic new way。
Summary of the invention
For overcoming above-mentioned the deficiencies in the prior art, the preparation method that it is an object of the invention to provide a kind of highly branched block polyether amino silicone finishing agent, it contains polyethers amido silicon oil highly branched, cancellated, for fabric treating, can give fabric better soft resilience。
For achieving the above object, the technical solution used in the present invention is: the preparation method of a kind of highly branched block polyether amino silicone finishing agent, comprises the following steps:
The first step, have in the reactor of thermometer, reflux condensing tube and motor stirrer at device, weigh linear α in proportion, polydimethylsiloxane (HPS) that ω-dimethyl hydrogen is silicone terminated and molecule include oligomeric hydrogeneous (sesquialter) siloxanes (HPOS) of multiple Si--H bond, Si--H bond degree of functionality >=3, it is uniformly mixed, is denoted as raw material A；Then, it is 1 by Si--H bond contained in raw material A with C=C double bond mol ratio in allylic epoxide (being denoted as raw material B):The ratio of 1-1.05 adds raw material B, stirring and evenly mixing, then, leads to N2Protect, be heated to 75-100o С and under platinum catalyst effect, be made directly hydrosilylation addition reaction or carry out hydrosilylation addition reaction 1-4h in small molecular alcohol solvent R1, obtain the blend (EPS) of the epoxy-modified polydimethylsiloxane of intermediate and epoxy-modified oligomeric (sesquialter) siloxanes；
Second step, in above-mentioned intermediate reaction system, is 1 by epoxy radicals contained in intermediate and polyetheramine mol ratio:The ratio of 0.5-1 adds polyetheramine and part organic solvent R2, polyetheramine is denoted as raw material C, intermediate is carried out aminolysis ring-opening reaction 3-10h with raw material C at 50-120o С, reaction terminates, decompression Distillation recovery partial solvent or addition solvent dilution make silicone oil reach 40-60%, obtaining transparency liquid, i.e. highly-branched block polyether amino silicone finishing agent, the content of its active component highly-branched block polyether amino silicone oil is about 40-60%。
Described linear α, the polydimethylsiloxane (HPS) that ω-dimethyl hydrogen is silicone terminated, shown in structure such as formula (1), Si--H bond content is that 0.01-0.08%, content represent with the molal quantity of Si--H bond contained in every 100gHPS, n=32-268, mean molecule quantity (Mn)=2500-20000:
Described oligomeric hydrogeneous (sesquialter) siloxanes (HPOS), for in structure containing multiple chain link shown in formula (2) (a)-(f), structure height branching oligomeric containing hydrogen silsesquioxane (having another name called Silicon Containing Hydrogen resin) or for structure contains the α containing S-H key in chain link, end group and main chain shown in formula (2) (a), formula (2) (d), formula (2) (e) simultaneously, the polymethyl hydrogen siloxane that s-dimethyl hydrogen is silicone terminated, R=methyl, ethyl, octyl group, cetyl, octadecyl or phenyl group in formula (2)；The Si-H content of described oligomeric hydrogeneous (sesquialter) siloxanes (HPOS) is 0.02-0.8%, content represents with the molal quantity of Si--H bond contained in every 100gHPOS, viscosity is 0.1-10.0Pa.s, consumption is linear α, the 3-15% of the polydimethylsiloxane HPS mass that ω-dimethyl hydrogen is silicone terminated, can from such as Zhejiang Run He new material company limited of relevant producer both at home and abroad, Dongguan City Xin Runlai Electronic Science and Technology Co., Ltd., U.S. DowCorning(Shanghai) company limited, Pinghu associating Chemical Co., Ltd. buy:
Described raw material B is the organic compound simultaneously containing pi-allyl and epoxy radicals in molecule。
It is CH that described raw material B includes allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate and structure2=CHCH2O(C2H4O) a (C3H6O) b CH2CH(O)CH2Allyl polyethenoxy polyethenoxy ether epoxide in the mixture of any one or two kinds, in formulaa、bValue is 0,1,2,3...... positive integer respectively,a+b=5-20, the mean molecule quantity of allyl polyethenoxy polyoxypropylene epoxide is 300-1000。
Described allyl polyethenoxy polyethenoxy ether epoxide includes allyl polyethenoxy polyoxypropylene epoxy radicals ether, allyl polyethenoxy epoxy radicals ether, pi-allyl polyoxypropylene epoxy radicals ether。
Described polyetheramine, is connected with primary amino radical, the middle binary organic amine for polyether segment for end group, shown in structure such as formula (3-1), (3-2):
Described polyether segment includes polyoxyethylene poly-oxygen propylene aether, polyoxyethylene ether, polyethenoxy ether。
Described polyetheramine includes polyetheramine ED-600, ED-900, ED-2003 and polyetheramine D-230, D-400, D-2000 series of products, and average molecular weight range is 230-2000；Can buy from Yangzhou morningization science and technology group and Huntsman company, preferentially choose the polyetheramine that Huntsman company produces。
Described small molecular alcohol solvent R1 is ethanol, isopropanol, the tert-butyl alcohol；Described organic solvent R2, for the mixture of small molecular alcohol, alcohol ether or the two arbitrary proportion；Described organic solvent R2 includes ethanol, isopropanol, the tert-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol, butyl glycol ether, glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propandiol butyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol butyl oxide；Small molecular alcohol solvent R1+ organic solvent R2 consumption is the 30-200% of raw material A+raw material B+ raw material C total amount。
Described catalyst is chloroplatinic acid or complexation platinum, and consumption is 50ppm。
Described highly-branched block polyether amino silicone oil is the poly organo alkyl copolymer containing chain link shown in formula (4) (A)-Shi (E) or segment:
Described highly-branched block polyether amino silicone finishing agent, active component highly-branched block polyether amino silicone oil content is 40-60%, and all the other components are organic solvent；
Described highly-branched block polyether amino silicone finishing agent, the transparent shape of outward appearance, the isomerous tridecanol polyoxyethylene ether emulsifying agent of silicone oil quality 5-30% need to be added during use, and under high shear mechanical agitation and deionized water effect, it is made into transparent ~ translucent microemulsion that solid content is 15%, it is diluted being made into arrangement work body lotion in the ratio of+100 parts of water of 2 parts of microemulsion again, then by textile swatch in arranging an immersing and rolling in body lotion, take out, fabric dries 5min at 100-105o С, 160o С shapes 1.5-3.0min, again at equilibrium at room temperature 30min, comfortable feel and desirably soft resilience can be obtained。
Beneficial effects of the present invention: the present invention is by linear α, polydimethylsiloxane (HPS) and molecule that ω-dimethyl hydrogen is silicone terminated include multiple Si--H bond (Si--H bond degree of functionality >=3), highly branched oligomeric hydrogeneous (sesquialter) siloxanes (HPOS) of molecular structure is blended is made into initial action raw material A, then under platinum catalyst effect, again raw material A and pi-allyl epoxide (raw material B) are carried out hydrosilylation addition reaction, first synthetic intermediate molecular structure contains the blend of linearly epoxy-modified polydimethylsiloxane and epoxy-modified highly-branched oligomeric (sesquialter) siloxanes simultaneously；Then, again intermediate and binary polyetheramine are carried out aminolysis open loop in organic solvent, directly oligomeric for highly-branched (sesquialter) siloxane chain paragraph key is incorporated into or embed in polyethers amino silicone structure with the ring-opening reaction of linear epoxy radicals modified dimethyl polysiloxane and epoxy-modified oligomeric (sesquialter) siloxanes by linear binary polyetheramine simultaneously, not only can realize the highly branched of target product block polyether amino silicone oil structure, and the block polyether amino silicone oil film property synthesized by this method obtains useful improvement, therefore for the soft Final finishing of fabric, not only soft smooth comfortable, and fabric resilience is good。
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not restricted to these embodiments。
Embodiment 1: there is in the there-necked flask of thermometer, reflux condensing tube and motor stirrer to be sequentially added in proportion 95gSi-H linkage content to be 0.01% at device, the α of Mn=20000, the polydimethylsiloxane (HPS) that ω-dimethyl hydrogen is silicone terminated, 5gSi-H content is netted oligomeric containing the hydrogeneous MQ resin (HPOS) of hydrogen silsesquioxane containing the highly-branched of R=H in formula (2) (a), formula (2) (c), formula (2) (e) and formula (2) (f) four kinds of chain links, formulas in 0.8% structure, mechanical agitation mix homogeneously, is denoted as raw material A；Then, 5.64g allyl glycidyl ether (raw material B), stirring and evenly mixing, logical N are added in Si--H bond contained in raw material A and the ratio that C=C double bond mol ratio is 1:12Protection; it is heated to 75o С; add 50ppm chloroplatinic acid temperature control 80o С and react 4h; it is down to room temperature; obtain total amount and be about 105.64g colourless transparent liquid; namely polydimethylsiloxane/oligomeric silsesquioxane blend (being denoted as intermediate E PS-1) that intermediate 2,3-epoxypropoxy is modified, the total amount containing epoxy radicals is about 0.0495mol；
In above-mentioned intermediate E PS-1 system, the butyl glycol ether solvent be ratio adds 5.70g, mean molecule quantity is 230 the polyetheramine D230 (raw material C) and 33.4g of 1:0.5, consumption being raw material A+raw material B+ raw material C total amount 30% in epoxy radicals contained in EPS-1 and polyetheramine mol ratio, stirring and evenly mixing, then, reheating is warming up to 120 DEG C of reaction 3h, it is down to room temperature, add 40.8g butyl glycol ether solvent to be diluted, obtain colourless transparent liquid, i.e. highly-branched block polyether amino silicone finishing agent (HBPS-230), active component content is 60%。
Embodiment 2: there is thermometer at device, being sequentially added into 85.0gSi-H linkage content in the there-necked flask of reflux condensing tube and motor stirrer in proportion is 0.08%, the α of Mn2500, the polydimethylsiloxane (HPS) that ω-dimethyl hydrogen is silicone terminated, 15.0gSi-H content is containing formula (2) (a) in 0.2% structure, formula (2) (b) and three kinds of chain links of formula (2) (d), R=H in formula, viscosity is oligomeric containing hydrogen silsesquioxane (HPOS) for the highly-branched resin-like of PolydimethylsiloxaneChain Chain section in the middle of 1.75Pa.s, mechanical agitation mix homogeneously, it is denoted as raw material A；Then, then add 11.70g allyl glycidyl ether (raw material B), stirring and evenly mixing in Si--H bond contained in raw material A with the ratio that C=C double bond mol ratio is 1:1.05, lead to N2Protection; it is heated to 80o С; add 50ppm chloroplatinic acid and temperature control 85o С reacts 1h; then when 85o С, 500mmHg, decompression steams residual raw materials B; be down to room temperature, obtain total amount and be about 111.17g colourless transparent liquid, i.e. intermediate 2; the mixture (being denoted as EPS-2) of polydimethylsiloxane/oligomeric silsesquioxane that 3-epoxypropoxy is modified, is 0.098mol containing epoxy radicals total amount；
In above-mentioned intermediate E PS-2 system, add the polyetheramine ED-600 (raw material C) and 85.0g of 58.8g, Mn=600 in epoxy radicals contained in EPS-2 and the ratio that polyetheramine mol ratio is 1:1, consumption is raw material A+isopropanol solvent of raw material B+ raw material C total amount 50%, stirring and evenly mixing, then, reheating is warming up to 80 DEG C of reaction 3h, it is down to room temperature, add the dilution of 85.0g butyl glycol ether, obtain colourless transparent liquid, i.e. highly-branched block polyether amino silicone finishing agent (HBPS-600), the content of active component highly-branched block polyether amino silicone oil is 50%。
Embodiment 3: have in the there-necked flask of thermometer, reflux condensing tube and motor stirrer at device and be sequentially added into the α that 90.0gSi-H linkage content is 0.02% in proportion, the polydimethylsiloxane HPS that ω-dimethyl hydrogen is silicone terminated, 10.0gSi-H content is containing the highly-branched phenyl hydrogeneous MQ resin of hydrogeneous oligomeric silsesquioxane phenyl of R=phenyl in formula (2) (a), formula (2) (b), formula (2) (d) and formula (2) (e) four kinds of chain links, formulas in 0.3% structure, mechanical agitation mix homogeneously, is denoted as raw material A；Then, 6.80g methyl propenoic acid glycidyl ether-ether (raw material B), stirring and evenly mixing, logical N are added in Si--H bond contained in raw material A and the ratio that C=C double bond mol ratio is 1:12Protection; it is heated to 80o С; add 50ppm chloroplatinic acid catalyst temperature control 90o С and react 3h; it is down to room temperature; obtain total amount and be about 106.8g colourless transparent liquid; the i.e. blend (being denoted as EPS-3) of intermediate 2,3-epoxy the third oxygen propionyloxy modified dimethyl polysiloxane/oligomeric silsesquioxane, the total amount containing epoxy radicals is about 0.048mol；
In above-mentioned intermediate E PS-3 system, 28.08g is added with the ratio that polyetheramine mol ratio is 1:0.65 in epoxy radicals contained in EPS-3, the polyetheramine ED-900 (raw material C) of Mn=900 and 89.92g, consumption is isopropanol-propandiol butyl ether (mass ratio of isopropanol and propandiol butyl ether the is 7:3) mixed solvent of raw material A+raw material B+ raw material C total amount 66.6%, stirring and evenly mixing, then, reheating is warming up to 90 DEG C of reaction 8h, it is down to room temperature, obtain colourless transparent liquid, i.e. highly-branched block polyether amino silicone finishing agent (HBPS-900), active component content is 60%。
Embodiment 4: have in the there-necked flask of thermometer, reflux condensing tube and motor stirrer at device and be sequentially added into the α that 90.0gSi-H linkage content is 0.015% in proportion, the polydimethylsiloxane (HPS) that ω-dimethyl hydrogen is silicone terminated, 10.0gSi-H content is containing R=C in formula (2) (a), formula (2) (b), formula (2) (d), formula (2) (e) and formula (2) (f) five kinds of chain links, formulas in 0.3% structure16H33, viscosity be the highly-branched hydrogeneous oligomeric silsesquioxane of netted cetyl (having another name called the hydrogeneous MQ silicones of cetyl) of 1.74Pa.s, mechanical agitation mix homogeneously, be denoted as raw material A；Then, raw material B 3.0g allyl glycidyl ether (raw material B is added in Si--H bond contained in raw material A with the ratio that C=C double bond mol ratio is 1:11) and 5.20g, Mn=300 allyl polyethenoxy epoxy radicals ether (raw material B2) mixture and 10.8g isopropanol solvent, be uniformly mixed, logical N2Protection; it is heated to 80o С; add 50ppm chloroplatinic acid catalyst temperature control 80-85o С and react 2.5h; it is down to room temperature; obtain total amount and be about 119.0g colourless transparent liquid; the mixture (EPS-4) of the polydimethylsiloxane that namely intermediate 2,3-glycidoxypropyl group/epoxidized polyether base modifiies altogether/cetyl silsesquioxane oligomer, the total amount containing epoxy radicals is about 0.0435mol；
In above-mentioned intermediate system, in contained epoxy radicals and the ratio that polyetheramine mol ratio is 1:0.6 add polyetheramine ED-900 (the raw material C of raw material C 11.75g, Mn=9001) and polyetheramine ED-2003 (the raw material C of 26.0g, Mn=20002) and isopropanol-butyl glycol ether solvent (isopropanol and butyl glycol ether mass ratio are 8:2) that 208.1g, consumption are raw material A+raw material B+ raw material C total amount 150%, stirring and evenly mixing, then, reheating is warming up to 85 DEG C of reaction 10h, it is down to room temperature, obtain colourless transparent liquid, i.e. highly-branched block polyether amino silicone finishing agent (HBPS-900/2003), active component content about 40%。
Embodiment 5: the α that Si--H bond content is 0.03% being sequentially added into 92.0g in the there-necked flask of thermometer, reflux condensing tube and motor stirrer in proportion is had at device, the polydimethylsiloxane (HPS) that ω-dimethyl hydrogen is silicone terminated, the Si-H content of 8.0g is containing R=-C in formula (2) (a), formula (2) (d), formula (2) (e) and formula (2) (f) four kinds of chain links, formulas in 0.25% structure2H5, viscosity be the silicone terminated oligomeric ethyl hydrogen-containing siloxane of α, the s-dimethyl hydrogen of 0.125Pa.s, mechanical agitation mix homogeneously, be denoted as raw material A；Then, add the allyl polyethenoxy epoxy radicals ether (raw material B) of 48.08g, Mn=1000 and 44.4g in Si--H bond contained in raw material A and the ratio that C=C double bond mol ratio is 1:1.01, consumption is the alcohol solvent of raw material A+raw material B total amount 30%, stirring and evenly mixing, logical N2Protection; it is heated to 95o С; add 50ppm chloroplatinic acid catalyst and carry out hydrosilylation addition reaction 2h; it is down to room temperature; obtain total amount and be about 192.48g light brown clear liquid; the alcoholic solution of the polydimethylsiloxane that namely the glycidoxy polyoxyethylene ether containing 148.08g intermediate 2,3-modifiies altogether/low PES-4 (EPS-5), intermediate epoxy group content is about 0.0476mol；
In above-mentioned intermediate system, add raw material C 14.28g, Mn=600 polyetheramine ED-600 (raw material C in epoxy radicals contained in intermediate with the ratio that polyetheramine mol ratio is 1:0.81) and polyetheramine ED-900 (the raw material C of 21.42g, Mn=9002) and isopropanol-Propylene Glycol Dimethyl Ether (isopropanol and Propylene Glycol Dimethyl Ether mass ratio are 5:5) solvent that 55.13g, consumption are raw material A+raw material B+ raw material C total amount 30%, stirring and evenly mixing, then, reheating is warming up to about 85 DEG C reaction 8h, it is down to room temperature, adds 84.0g butyl glycol ether agitation and dilution, obtain colourless transparent liquid, i.e. highly-branched block polyether amino silicone finishing agent (HBPEPS-600/900), active component content about 50%。
Example 1-5 highly-branched block polyether amino silicone finishing agent, adjusts pH to be about 6 with acetic acid, adds isomerous tridecanol polyoxyethylene ether 1390 stirring and evenly mixing of silicone oil quality 10%, stir and add water emulsification, prepare into the silicon microemulsion that solid content is 15%；Take the silicon microemulsion that 2g solid content is 15% again, be made into arrangement work body lotion with the dilution of 100g water；Separately taking area is 16.3cm × 12.6cm(warp × latitude) the textile embryo cloth (specification 21 × 21 × 108 × 98) of white, it is dipped in work body lotion and arranges by laboratory room small-sized padding machine one immersing and rolling, pick-up about 70%, then by fabric 100 DEG C dry 5min, at 160 DEG C of baked and cured 90s, again at equilibrium at room temperature 24h, carry out performance test；Flexibility represents with bending stiffness, measures with DC-RRY1000 type computer observing and controlling pliability instrument, and resilience creasy recovery angle analyzer measures, and feel digital palpation for examination of trauma is evaluated。
Preparing with method in another Example 1-5 but do not add the block polyether amino silicone prepared by hydrogeneous oligomeric silsesquioxane copolymer and be used as the reference of the present invention, the application performance measurement result of the bafta arranged is in Table 1。
。
Claims (10)
1. the preparation method of block polyether amino silicone finishing agent one kind highly branched, it is characterised in that include following steps:
The first step, have in the reactor of thermometer, reflux condensing tube and motor stirrer at device, weigh linear α in proportion, polydimethylsiloxane (HPS) that ω-dimethyl hydrogen is silicone terminated and molecule include oligomeric hydrogeneous (sesquialter) siloxanes (HPOS) of multiple Si--H bond, Si--H bond degree of functionality >=3, it is uniformly mixed, is denoted as raw material A；Adding raw material B in Si--H bond contained in raw material A with the ratio that C=C double bond mol ratio in allylic epoxide is 1:1-1.05, allylic epoxide is as raw material B, stirring and evenly mixing；Logical N2Protect, be heated to 75-100o С and under catalyst action, be made directly hydrosilylation addition reaction or carry out hydrosilylation addition reaction 1-4h in small molecular alcohol solvent R1; obtain intermediate (EPS); intermediate (EPS) is the blend of linear α, ω-epoxy-modified polydimethylsiloxane Yu epoxy-modified oligomeric (sesquialter) siloxanes；
Second step, in above-mentioned intermediate (EPS) reaction system, is 1 by epoxy radicals contained by intermediate (EPS) and polyetheramine mol ratio:The ratio of 0.5-1 adds polyetheramine and organic solvent R2, polyetheramine is denoted as raw material C, intermediate (EPS) is carried out aminolysis ring-opening reaction 3-10h with raw material C at 50-120o С, reaction terminates, decompression Distillation recovery partial solvent or addition organic solvent R2 dilution make silicone oil reach 40-60%, obtaining transparency liquid, i.e. highly-branched block polyether amino silicone finishing agent, the content of its active component highly-branched block polyether amino silicone oil is 40-60%。
2. the preparation method of a kind of highly-branched block polyether amino silicone finishing agent according to claim 1, it is characterised in that described small molecular alcohol solvent R1 is ethanol, isopropanol, the tert-butyl alcohol；The described mixture that organic solvent R2 is small molecular alcohol, alcohol ether or the two arbitrary proportion；Small molecular alcohol solvent R1+ organic solvent R2 consumption is the 30-200% of raw material A+raw material B+ raw material C total amount。
3. the preparation method of a kind of highly-branched block polyether amino silicone finishing agent according to claim 1, it is characterized in that, described linear α, the polydimethylsiloxane (HPS) that ω-dimethyl hydrogen is silicone terminated, shown in structure such as formula (1), representing with the molal quantity of Si--H bond contained in every 100gHPS, Si--H bond content is 0.01-0.08%, n=32-268, average molecular mass Mn=2500-20000；
Described oligomeric hydrogeneous (sesquialter) siloxanes (HPOS), for structure containing hydrogen silsesquioxane or be contain formula (2) (a) in structure containing multiple chain link shown in formula (2) (a)-Shi (2) (f) oligomeric, formula (2) (d), chain link shown in formula (2) (e), end group and main chain contain the α of S-H key simultaneously, the polymethyl hydrogen siloxane that s-dimethyl hydrogen is silicone terminated, represent with the molal quantity of Si--H bond contained in every 100gHPOS, Si-H content is 0.02-0.8%, viscosity is 0.1-10.0Pa.s, consumption is linear α, the 3-15% of the polydimethylsiloxane quality that ω-dimethyl hydrogen is silicone terminated, R=methyl in formula (2), ethyl, octyl group, cetyl, octadecyl, phenyl group:
。
4. the preparation method of a kind of highly-branched block polyether amino silicone finishing agent according to claim 1, it is characterised in that described raw material B is the organic compound simultaneously containing pi-allyl and epoxy radicals in molecule。
5. the preparation method of a kind of highly-branched block polyether amino silicone finishing agent according to claim 4, it is characterised in that it is CH that described raw material B includes allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate and structure2=CHCH2O(C2H4O) a (C3H6O) b CH2CH(O)CH2Allyl polyethenoxy polyethenoxy ether epoxide in the mixture of any one or two kinds, in formulaa、bValue is 0,1,2,3...... positive integer respectively,a+b=5-20, the mean molecule quantity of allyl polyethenoxy polyoxypropylene epoxide is 300-1000；
Described allyl polyethenoxy polyethenoxy ether epoxide includes allyl polyethenoxy polyoxypropylene epoxy radicals ether, allyl polyethenoxy epoxy radicals ether, pi-allyl polyoxypropylene epoxy radicals ether。
6. the preparation method of a kind of highly-branched block polyether amino silicone finishing agent according to claim 1, it is characterized in that, described polyetheramine is that end group is connected with primary amino radical, the middle binary organic amine for polyether segment, shown in structure such as formula (3-1), (3-2):
。
7. the preparation method of a kind of highly-branched block polyether amino silicone finishing agent according to claim 6, it is characterised in that described polyether segment includes polyoxyethylene poly-oxygen propylene aether, polyoxyethylene ether, polyethenoxy ether。
8. the preparation method of a kind of highly-branched block polyether amino silicone finishing agent according to claim 1, it is characterized in that, described polyetheramine includes polyetheramine ED-600, ED-900, ED-2003 and polyetheramine D-230, D-400, D-2000 series of products, and average molecular weight range is 230-2000。
9. the preparation method of a kind of highly-branched block polyether amino silicone finishing agent according to claim 1, it is characterised in that described catalyst is chloroplatinic acid or complexation platinum, and consumption is 50ppm。
10. the preparation method of a kind of highly-branched block polyether amino silicone finishing agent according to claim 1, it is characterized in that, described highly-branched block polyether amino silicone oil is the poly organo alkyl copolymer containing chain link shown in formula (4) (A)-Shi (E) or segment:
。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543445A (en) * | 2016-11-03 | 2017-03-29 | 江苏海云花新材料有限公司 | Super soft and smooth silicone oil of a kind of SRS D9 types and preparation method thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675652A (en) * | 2012-05-18 | 2012-09-19 | 陕西科技大学 | Preparation method of crosslinking-modified pectinate polyether amino-silicone oil |
| CN102911365A (en) * | 2012-11-12 | 2013-02-06 | 浙江汉邦化工有限公司 | Method for preparing modified block polyether amino silicone oil |
| CN102911363A (en) * | 2012-11-02 | 2013-02-06 | 浙江汉邦化工有限公司 | Preparation method for nitrogenous silane coupling agent blocked polyether block silicone oil |
| CN102964602A (en) * | 2012-11-27 | 2013-03-13 | 陕西科技大学 | Preparation method of steric hindered amine polyether-group polysiloxane |
| CN103937001A (en) * | 2014-03-28 | 2014-07-23 | 陕西科技大学 | Method for preparing water-dispersible alkyl/polyether amino-silicon resin |
| CN104371107A (en) * | 2014-10-28 | 2015-02-25 | 深圳市红叶杰科技有限公司 | Hydrogen-containing MQ silicon resin and preparation method thereof |
| CN104530434A (en) * | 2014-12-18 | 2015-04-22 | 上海雅运纺织助剂有限公司 | Organosilicon polymer and synthesis method thereof |
-
2016
- 2016-02-06 CN CN201610087133.6A patent/CN105694046A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675652A (en) * | 2012-05-18 | 2012-09-19 | 陕西科技大学 | Preparation method of crosslinking-modified pectinate polyether amino-silicone oil |
| CN102911363A (en) * | 2012-11-02 | 2013-02-06 | 浙江汉邦化工有限公司 | Preparation method for nitrogenous silane coupling agent blocked polyether block silicone oil |
| CN102911365A (en) * | 2012-11-12 | 2013-02-06 | 浙江汉邦化工有限公司 | Method for preparing modified block polyether amino silicone oil |
| CN102964602A (en) * | 2012-11-27 | 2013-03-13 | 陕西科技大学 | Preparation method of steric hindered amine polyether-group polysiloxane |
| CN103937001A (en) * | 2014-03-28 | 2014-07-23 | 陕西科技大学 | Method for preparing water-dispersible alkyl/polyether amino-silicon resin |
| CN104371107A (en) * | 2014-10-28 | 2015-02-25 | 深圳市红叶杰科技有限公司 | Hydrogen-containing MQ silicon resin and preparation method thereof |
| CN104530434A (en) * | 2014-12-18 | 2015-04-22 | 上海雅运纺织助剂有限公司 | Organosilicon polymer and synthesis method thereof |
Cited By (13)
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| CN106693829A (en) * | 2016-12-29 | 2017-05-24 | 柏青龙 | Modified composite type surface active agent |
| CN107602865A (en) * | 2017-09-26 | 2018-01-19 | 上海应用技术大学 | A kind of three cationic silicones surfactants and preparation method thereof |
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| CN110093782B (en) * | 2019-05-29 | 2021-05-18 | 杭州美高华颐化工有限公司 | Preparation method of low-foam silicon-containing degreasing agent |
| CN110093782A (en) * | 2019-05-29 | 2019-08-06 | 杭州美高华颐化工有限公司 | A kind of preparation method of the low siliceous degreaser of bubble |
| CN110172154A (en) * | 2019-06-03 | 2019-08-27 | 浙江工业大学 | A kind of amino-modified silicone oil and preparation method thereof containing chain alkyl |
| CN111499872A (en) * | 2020-04-29 | 2020-08-07 | 杭州美高华颐化工有限公司 | Preparation method of side chain hydrophilic modified block silicone oil for cotton |
| CN111499872B (en) * | 2020-04-29 | 2021-08-24 | 杭州美高华颐化工有限公司 | Preparation method of side chain hydrophilic modified block silicone oil for cotton |
| CN113174031A (en) * | 2021-06-10 | 2021-07-27 | 哈尔滨工程大学 | Nano-body curing agent with internal toughening function and preparation method thereof |
| CN113336953A (en) * | 2021-06-21 | 2021-09-03 | 宁波润禾高新材料科技股份有限公司 | Modified polyether amine, and preparation method and application thereof |
| CN113717388A (en) * | 2021-08-19 | 2021-11-30 | 浙江三元纺织有限公司 | Preparation of ecological antibacterial finishing agent and method for finishing fabric by using same |
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