CN102660029A - Cation modified supersoft hydrophilic block silicone oil compound and preparation method and application - Google Patents
Cation modified supersoft hydrophilic block silicone oil compound and preparation method and application Download PDFInfo
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Abstract
The invention relates to the field of textile finishing agents, in particular to a cation modified supersoft hydrophilic block silicone oil compound and a preparation method and application. The cation modified supersoft hydrophilic block silicone oil compound has a cation having the following structural formula, wherein n1 is 5 to 10, R is shown in the accompanying drawing, a is 0 to 3, b is 0 to 3, and n is 10 to 40. The cation modified supersoft hydrophilic block silicone oil compound synthesized by the invention is suitable for hand feeling finishing of textiles consisting of one or more fibers such as cotton, polyester, nylon and acrylic fiber, has softer, slipperier and fluffier effects than an amino silicone oil, has more excellent stability such as acid and alkali resistance, electrolyte resistance, high temperature resistance and shear resistance, and thoroughly solves the problems of easy demulsification, floating oil, roller sticking and difficulty in rehandling of the traditional amino silicone oil.
Description
Technical field
The present invention relates to the textile finish field, relate in particular to a kind of cation-modified ultra soft hydrophilic block silicon oil compound and preparation method and application.
Background technology
In the hand feel finishing agent of textiles, need to use amido silicon oil more than 80% in the market.Amido silicon oil is the modified silicon oil that grow up the eighties in last century a kind of is mainly used in softness, fluffy, smooth hand arrangement; Its molecular backbone chain is to form with the Si-O key with excellent flexibility; Introduced the amino of different structure on the side chain according to different amino silicane coupling agents; Amino has chemical propertys such as stronger polarity, reactivity, adsorptivity, thereby has given amido silicon oil geneogenous advantage on the fabric feeling finishing effect.But amido silicon oil can not directly use, and must add and could use after emulsifying agent is emulsified into emulsion.Through technical development for many years; The selection of amido silicon oil emulsifying agent, the aspects such as optimization of emulsifying process have obtained changing completely; But still can not from solve the amido silicon oil use in essence, be prone to problems such as breakdown of emulsion, floating oil, roll banding, sticking cylinder, easy generation silicone oil spot; Simultaneously, the introducing of the highly active amino of side chain has caused fabric to be prone to a series of problems such as fabric after look change, xanthochromia, the processing can not return something for repairs.In recent years; The block silicone oil of substituted-amino silicone oil product progressively comes into vogue on market; But because the raw material dependence on import of synthetic operation more complicated, key; Particularly can not 100% in the addition process of silicon hydrogen and glycidyl allyl ether transform, cause that in the market block silicone oil quality is unstable, cost is higher; Selectable Amino Terminated polyether(ATPE) kind is limited simultaneously, causes the scope of application of block silicone oil narrower, in the hand feel finishing of various fabrics, can't embody the effect that amido silicon oil has; Simultaneously in the synthetic process, adopted a large amount of volatile solvents, though harmless, back arrangement processing environment has been brought many detrimentally affects.
Publication number is the preparation method that the patent of invention of CN101497697A discloses a kind of block water-soluble silicon oil; Method has comprised that the amidation of amino coupling agent, preparation, the preparation of polysiloxane-polyether linear block copolymers and the ammonia of segmented copolymer of the hydrogeneous methylsiloxane midbody of end four preparation processes such as separates; Entire synthesis process relates to a plurality of heterogeneous chemical reactions; Stability influence to product quality is bigger; In the multiple conversion of amino, influenced amino activity, its treatment effect is descended significantly.
Publication number is the preparation method that the patent of invention of CN101497697A discloses a kind of poly organo alkylamino radical polyether block copolymer; Method has comprised α; ω-the preparation of hydrogen siloxane midbody, α, three steps of preparation of the preparation of ω-bicyclic oxygen ZGK 5 midbody, poly organo alkylamino radical polyether block copolymer, the synthetic product can solve the application deficiency that amido silicon oil exists preferably; But at α; In the building-up process of ω-bicyclic oxygen ZGK 5 midbody, epoxy group(ing) easy open loop under high temperature, tart condition has a strong impact on follow-up synthesizing, and then influences product quality stability.Adopted Amino Terminated polyether(ATPE) in the poly organo alkylamino radical polyether block copolymer building-up process; Amino Terminated polyether(ATPE) is mainly controlled by U.S. Huntsman Corporation at present; Product price is higher, of less types; The product cost that causes producing is higher, the scope of application is narrower, be mainly used in trevira hand feel finishing and on other fiber treatment effect relatively poor, so substituted-amino silicone oil all sidedly.
Summary of the invention
In order to solve above-mentioned technical problem; An object of the present invention is to provide a kind of cation-modified ultra soft hydrophilic block silicon oil compound; Second purpose of the present invention provides the preparation method of above-mentioned cation-modified ultra soft hydrophilic block silicon oil compound, and the 3rd purpose of the present invention provides the application of above-mentioned cation-modified ultra soft hydrophilic block silicon oil compound.The cation-modified ultra soft hydrophilic block silicon oil compound of synthetic of the present invention is applicable to the hand feel finishing of one or more fibrous fabrics of cotton, terylene, polyamide fibre, acrylic fibers; Has soft, sliding, the fluffy effect that surmounts amido silicon oil; Have more excellent acid and alkali-resistance, electrolyte-resistant, high temperature resistant, anti-shearing equistability, problem such as thoroughly solved easy breakdown of emulsion, floating oil, roll banding that traditional amido silicon oil exists, be difficult for returning something for repairs.
In order to realize first above-mentioned purpose, the technical scheme below the present invention has adopted:
Cation-modified ultra soft hydrophilic block silicon oil compound, this compound has the positively charged ion of following structural formula:
Described n1 is 5 ~ 10; Described R is
; A=0 ~ 3 wherein; B=0 ~ 3, n=10 ~ 40.
In order to realize second above-mentioned purpose, the technical scheme below the present invention has adopted:
The preparation method of cation-modified ultra soft hydrophilic block silicon oil compound, this method comprises the steps:
1) α, omega-amino-ZGK 5 intermediates preparation
With the octamethylcyclotetrasiloxane and 1 after the dehydration; 1,3,3-tetramethyl-two aminopropyl sily oxide add in the there-necked flask according to certain ratio; Open to stir and be warmed up between 90-95 ℃; Add temporary basic catalyst then, consumption is the 0.1-0.2% of octamethylcyclotetrasiloxane quality, between 90-95 ℃ insulation reaction 5-6 hour; Insulation is warmed up to about 130-140 ℃ after finishing, and is incubated 1 hour, and basic catalyst is fully decomposed; Vacuumize the low-boiling-point substance of pulling out in the reactant, between 140-150 ℃ of the temperature control, relative vacuum degree control-99.8--99.9KPa about, obtain the α of low boiling mixture content≤1%, omega-amino-ZGK 5 midbody;
2) end ring oxygen polyethers and α, the preparation method of omega-amino-ZGK 5 midbody block polymerization
With end ring oxygen polyethers, α, omega-amino-ZGK 5 midbody is according to the epoxy group(ing) mole number: amino mole number is that the ratio of 1:1.1-1:1.2 joins in the there-necked flask, adds organic solvent; Consumption is the 40%-50% of reactant total mass, after adding, opens and stirs; Fully stirred 20 ~ 30 minutes; Be warmed up to 80-85 ℃, insulation reaction 15-20 hour, get final product the organopolysiloxane polyether block copolymer of ZGK 5, amino, polyethers ternary block;
3) the cation-modified preparation method of organopolysiloxane polyether block copolymer
In step 2) on the basis of the organopolysiloxane polyether block copolymer of prepared ZGK 5, amino, polyethers ternary block; Add a certain amount of alkylating reagent monochloroethane; Stirring is warmed up to about 95-100 ℃, insulation reaction 3-4 hour, get final product ultra soft hydrophilic block silicone oil.
As further improvement, the temporary basic catalyst described in the described step 1) is (CH
3)
4NOH alkali glue or (n-C
4H
9)
4POH alkali glue.
As further improvement, described step 2) described organic solvent is one or several combination of Virahol, ethylene glycol monobutyl ether, ethylene glycol ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, Diethylene Glycol, dipropylene glycol.
The general structure of the end ring oxygen polyethers as further improvement, described step 2) is:
；
A=0-3 wherein, b=0-3, one or more end ring oxygen polyethers among the n=10-40.
In order to realize the 3rd above-mentioned purpose, the technical scheme below the present invention has adopted:
The agent of a kind of ultra soft hydrophilic block sillicon oil treatment, this finishing composition comprise above-mentioned ultra soft hydrophilic block silicon oil compound, and the weight ratio of described ultra soft hydrophilic block silicon oil compound is respectively 1% ~ 60%.
The present invention is owing to adopted above-mentioned technical scheme, and with respect to prior art, the present invention has the following advantages
1) the ultra soft hydrophilic block silicone oil of the present invention preparation adopt domesticly be prone to produce, be prone to buying, end ring oxygen polyethers various in style is a basic material; On the backbone structure of ZGK 5, successfully embed polyether segment with excellent wetting ability, kindliness; Product has excellent automatic emulsifying performance, hydrophilicity and materialization stability, problem such as thoroughly solved the easy breakdown of emulsion of traditional amido silicon oil, floating oil, roll banding, sticking cylinder, be prone to produce oil mark, be difficult for returning something for repairs;
2) the ultra soft hydrophilic block silicone oil of the present invention's preparation has carried out the alkylated cation modification on the basis of the organopolysiloxane polyether block copolymer of ZGK 5, amino, polyethers ternary block; Polarity, adsorptivity and the reactivity of product under the condition of less amino content, have further been improved; Can reduce the consumption of finishing composition significantly; And enlarged the scope of application of product; Various fibers all there is excellent finishing effect, has solved present block silicone oil in wool, cotton, the relatively poor problem of acrylic fabric feel; The raising of cationization degree gives ultra soft hydrophilic block silicone oil certain antibiotic, anti-static function, and the while can be given the fluffy feel as the distinguished eider down of fabric; Reactive hydrogen on the amino thoroughly obtains replacing through alkylated reaction, efficiently solves to be prone to xanthochromic problem under the amino hot conditions, handles the still less look change of back fabric, xanthochromia.
Embodiment
Below in conjunction with embodiment the present invention is described further, but the scope that the present invention requires to protect is not limited to the scope that embodiment explains.
Embodiment 1-1 α, the preparation of omega-amino-ZGK 5 midbody
In the 2000ml there-necked flask of constant speed electric mixer, TM is housed, 1,1,3 of the octamethylcyclotetrasiloxane (D4) of adding 1230g and 50 grams, 3-tetramethyl-two aminopropyl sily oxide, stirring is warmed up to about 90-95 ℃, adds 1.28g (CH then
3)
4NOH content is 10% (CH
3)
4NOH alkali glue, insulation reaction 6 hours, insulation is warmed up to 135 ℃ after finishing, and is incubated 1 hour, with catalyzer (CH
3)
4NOH fully decomposes, and slowly vacuumizes, and has a large amount of low-boiling-point substances to flow out, and is 150 ℃ in temperature, and the relative vacuum degree be-condition of 99.9KPa, pulled out low-boiling-point substance 1 hour, till not having the material outflow.The synthetic product is a colorless transparent viscous liquid, and the ammonia value is: 0.345mmol/g, viscosity is: 50-55cs, fugitive constituent is :≤1%.
Embodiment 1-2 α, ω--the preparation of amino silicones midbody
In the 2000ml there-necked flask of constant speed electric mixer, TM is housed, 1,1,3 of the octamethylcyclotetrasiloxane (D4) of adding 1640g and 50 grams, 3-tetramethyl-two aminopropyl sily oxide, stirring is warmed up to about 90-95 ℃, adds 1.7g (CH then
3)
4NOH content is 10% (CH
3)
4NOH alkali glue, insulation reaction 6 hours, insulation is warmed up to 135 ℃ after finishing, and is incubated 1 hour, with catalyzer (CH
3)
4NOH fully decomposes, and slowly vacuumizes, and has a large amount of low-boiling-point substances to flow out, and is 150 ℃ in temperature, and the relative vacuum degree be-condition of 99.9KPa, pulled out low-boiling-point substance 1 hour, till not having the material outflow.The synthetic product is a colorless transparent viscous liquid, and the ammonia value is: 0.26mmol/g, viscosity is: 100-110cs, fugitive constituent is :≤1%.
Embodiment 2-1 end ring oxygen polyethers and α, the preparation of omega-amino-ZGK 5 midbody block polymerization
In the 2000ml there-necked flask of constant speed electric mixer, TM is housed, add the α of 800g embodiment 1-1 preparation, (the pfpe molecule amount of end ring oxygen polyethers is 920 to the end ring oxygen polyethers of omega-amino-ZGK 5 midbody, 106g; A+b=3, n=14), the ethylene glycol monobutyl ether of 604g; Open to stir, fully stir 30 minutes after, slowly be warmed up to about 80-85 ℃; Insulation reaction 20 hours; Can get the organopolysiloxane polyether block copolymer of transparent flaxen ZGK 5, amino, polyethers ternary block, viscosity is 500-550cs, and solid content is 60 ± 1%.
Embodiment 2-2 end ring oxygen polyethers and α, the preparation of omega-amino-ZGK 5 midbody block polymerization
In the 2000ml there-necked flask of constant speed electric mixer, TM is housed, add the α of 800g embodiment 1-1 preparation, (the pfpe molecule amount of end ring oxygen polyethers is 1850 to the end ring oxygen polyethers of omega-amino-ZGK 5 midbody, 214g; A+b=3, n=34-36), the ethylene glycol monobutyl ether of 676g; Open to stir, fully stir 30 minutes after, slowly be warmed up to about 80-85 ℃; Insulation reaction 20 hours; Can get the organopolysiloxane polyether block copolymer of transparent flaxen ZGK 5, amino, polyethers ternary block, viscosity is 600-650cs, and solid content is 60 ± 1%.
Embodiment 2-3 end ring oxygen polyethers and α, the preparation of omega-amino-ZGK 5 midbody block polymerization
In the 2000ml there-necked flask of constant speed electric mixer, TM is housed, add the α of 800g embodiment 1-2 preparation, (the pfpe molecule amount of end ring oxygen polyethers is 920 to the end ring oxygen polyethers of omega-amino-ZGK 5 midbody, 96g; A+b=3, n=14), the ethylene glycol monobutyl ether of 597g; Open to stir, fully stir 30 minutes after, slowly be warmed up to about 80-85 ℃; Insulation reaction 20 hours; Can get the organopolysiloxane polyether block copolymer of transparent flaxen ZGK 5, amino, polyethers ternary block, viscosity is 800-850cs, and solid content is 60 ± 1%.
Embodiment 2-4 end ring oxygen polyethers and α, the preparation of omega-amino-ZGK 5 midbody block polymerization
In the 2000ml there-necked flask of constant speed electric mixer, TM is housed, add the α of 800g embodiment 1-2 preparation, (the pfpe molecule amount of end ring oxygen polyethers is 1850 to the end ring oxygen polyethers of omega-amino-ZGK 5 midbody, 193g; A+b=3, n=34-36), the ethylene glycol monobutyl ether of 662g; Open to stir, fully stir 30 minutes after, slowly be warmed up to about 80-85 ℃; Insulation reaction 20 hours; Can get the organopolysiloxane polyether block copolymer of transparent flaxen ZGK 5, amino, polyethers ternary block, viscosity is 875-900cs, and solid content is 60 ± 1%.
The cation-modified preparation of embodiment 3-1 organopolysiloxane polyether block copolymer
The monochloroethane that on the basis of accomplishing embodiment 2-1, directly adds 18g, after fully stirring, stirring is warmed up to about 95-100 ℃; Insulation reaction 4 hours; Get final product the ultra soft hydrophilic block silicone oil of faint yellow transparent viscous fluid, viscosity is 600cs, solid content is 60 ± 1%.
The cation-modified preparation of embodiment 3-2 organopolysiloxane polyether block copolymer
The monochloroethane that on the basis of accomplishing embodiment 2-2, directly adds 18g, after fully stirring, stirring is warmed up to about 95-100 ℃; Insulation reaction 4 hours; Get final product the ultra soft hydrophilic block silicone oil of faint yellow transparent viscous fluid, viscosity is 715cs, solid content is 60 ± 1%.
The cation-modified preparation of embodiment 3-3 organopolysiloxane polyether block copolymer
The monochloroethane that on the basis of accomplishing embodiment 2-3, directly adds 13.5g, after fully stirring, stirring is warmed up to about 95-100 ℃; Insulation reaction 4 hours; Get final product the ultra soft hydrophilic block silicone oil of faint yellow transparent viscous fluid, viscosity is 905cs, solid content is 60 ± 1%.
The cation-modified preparation of embodiment 3-4 organopolysiloxane polyether block copolymer
The monochloroethane that on the basis of accomplishing embodiment 2-4, directly adds 13.5g, after fully stirring, stirring is warmed up to about 95-100 ℃; Insulation reaction 4 hours; Get final product the ultra soft hydrophilic block silicone oil of faint yellow transparent viscous fluid, viscosity is 1000cs, solid content is 60 ± 1%.
The foregoing description 3-X (X=1-4) product of producing is carried out contrast and the physics of effect, the detection of chemicalstability:
1, the preparation of finishing composition
Get the prepared content of the foregoing description 3-X (X=1-4) and be 60% product 100g; Slowly add water while stirring, the amount of water is 500g, opens rare one-tenth content and be the emulsion of about 10% zona pellucida blue light; Add the 2g Glacial acetic acid min. 99.5 at last, the pH value is adjusted between the 5-6.
2, the application art of finishing composition
Handle fabric: cotton bleaching tWoven Fabrics, T/C bleaching looped fabric, wash bleaching looped fabric, terylene lint entirely
Treatment process: consumption 10g/L
3, the contrast of result of use
In the contrast of result of use, mainly carry out the mensuration of the contrast of feel, hydrophilic contrast, xanthochromia property.
3.1 the contrast of feel
The effect of the processing fabric of softening agent feels that through the mode that touches with hand composite factors such as loft after the fabric treating, pliability, rebound resilience and smooth degree estimate; It is 5 each grade that feel is divided into; Rank is high more good more; 5 grades best, and 1 grade minimum, and the feel level data has estimating with the hand touch of experience technician to draw through five in the table 1.
3.2 hydrophilic contrast
Drip 1 with standard dropper from the fabric face of highly sprawling to level from fabric 10cm and drip, measure 1 under the quiescent conditions and drip complete wetting, diffusion, used time of infiltration on fabric face, the used time is short more, explains that its hydrophilic effect is good more.
3.3 the mensuration of xanthochromia property
Bleached woven fabric (former cloth) before not handling through finishing composition is measured the whiteness of fabric face through the whiteness appearance; Fabric is handled fabric face is measured in the typing back through the whiteness appearance whiteness through finishing composition; Contrast through two whiteness values; Estimate the xanthochromia property of finishing composition, value difference is more little, and the yellowing resistance of finishing composition can be good more.
Table 1 result of use comparative evaluation
4, the detection of physics, chemicalstability
The evaluation of table 2 stability
Ratings data through table 1, table 2 can be found out; Adopt the synthetic ultra soft hydrophilic block silicone oil of end ring oxygen polyethers to handle and on fabric, have excellent gentle right, fluffy, smooth hand feeling; Give fabric certain hydrophilicity simultaneously, on bleached woven fabric, do not influence the whiteness of fabric especially basically; Aspect stable, have excellent heat-resisting, anti-shearing, acidproof, alkaline-resisting, salt tolerant, anti-hard water stability, have wide application field and wide application prospect, can thoroughly comprehensive substituted-amino silicone oil.
Claims (6)
1. cation-modified ultra soft hydrophilic block silicon oil compound is characterized in that this compound has the positively charged ion of following structural formula:
；
Described n1 is 5 ~ 10; Described R is
; A=0 ~ 3 wherein; B=0 ~ 3, n=10 ~ 40.
2. a preparation method who prepares the described cation-modified ultra soft hydrophilic block silicon oil compound of claim 1 is characterized in that this method comprises the steps:
1) α, omega-amino-ZGK 5 intermediates preparation
With the octamethylcyclotetrasiloxane and 1 after the dehydration; 1,3,3-tetramethyl-two aminopropyl sily oxide add in the there-necked flask according to certain ratio; Open to stir and be warmed up between 90-95 ℃; Add temporary basic catalyst then, consumption is the 0.1-0.2% of octamethylcyclotetrasiloxane quality, between 90-95 ℃ insulation reaction 5-6 hour; Insulation is warmed up to about 130-140 ℃ after finishing, and is incubated 1 hour, and basic catalyst is fully decomposed; Vacuumize the low-boiling-point substance of pulling out in the reactant, between 140-150 ℃ of the temperature control, relative vacuum degree control-99.8--99.9KPa about, obtain the α of low boiling mixture content≤1%, omega-amino-ZGK 5 midbody;
2) end ring oxygen polyethers and α, the preparation method of omega-amino-ZGK 5 midbody block polymerization
With end ring oxygen polyethers, α, omega-amino-ZGK 5 midbody is according to the epoxy group(ing) mole number: amino mole number is that the ratio of 1:1.1-1:1.2 joins in the there-necked flask, adds organic solvent; Consumption is the 40%-50% of reactant total mass, after adding, opens and stirs; Fully stirred 20 ~ 30 minutes; Be warmed up to 80-85 ℃, insulation reaction 15-20 hour, get final product the organopolysiloxane polyether block copolymer of ZGK 5, amino, polyethers ternary block;
3) the cation-modified preparation method of organopolysiloxane polyether block copolymer
In step 2) on the basis of the organopolysiloxane polyether block copolymer of prepared ZGK 5, amino, polyethers ternary block; Add a certain amount of alkylating reagent monochloroethane; Stirring is warmed up to about 95-100 ℃, insulation reaction 3-4 hour, get final product ultra soft hydrophilic block silicone oil.
3. the preparation method of ultra soft hydrophilic block silicone oil midbody compound according to claim 3, it is characterized in that: the basic catalyst described in the step 1) is (CH
3)
4NOH alkali glue or (n-C
4H
9)
4POH alkali glue.
4. the preparation method of ultra soft hydrophilic block silicone oil midbody compound according to claim 3 is characterized in that: step 2) described organic solvent is one or several combination of Virahol, ethylene glycol monobutyl ether, ethylene glycol ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, Diethylene Glycol, dipropylene glycol.
5. the preparation method of ultra soft hydrophilic block silicone oil midbody compound according to claim 3 is characterized in that: step 2) described in the general structure of end ring oxygen polyethers be:
A=0-3 wherein, b=0-3, one or more end ring oxygen polyethers among the n=10-40.
6. ultra soft hydrophilic block sillicon oil treatment agent, this finishing composition comprise the described cation-modified ultra soft hydrophilic block silicon oil compound of claim 1, and the weight ratio of described cation-modified ultra soft hydrophilic block silicon oil compound is respectively 1% ~ 60%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949468A (en) * | 2016-06-23 | 2016-09-21 | 杭州传化精细化工有限公司 | Preparation method for anionic linear copolymerized organic silicon softening and finishing agent |
| CN106397776A (en) * | 2016-08-30 | 2017-02-15 | 浙江科峰有机硅有限公司 | Double amino type block polyether amino silicone oil and preparation method thereof |
| CN108951154A (en) * | 2018-05-23 | 2018-12-07 | 绍兴柯桥德美精细化工有限公司 | A kind of environment-friendly type terylene soft fabric, water repellent, anti-static multifunctional method for sorting |
| CN109280173A (en) * | 2018-09-13 | 2019-01-29 | 浙江润禾有机硅新材料有限公司 | A kind of super soft hydrophilic silicone oil and preparation method thereof |
| CN111171267A (en) * | 2020-01-20 | 2020-05-19 | 宁波润禾高新材料科技股份有限公司 | High-elasticity resin modified silicone oil and preparation method thereof |
| CN114230797A (en) * | 2021-12-30 | 2022-03-25 | 江苏奥斯佳材料科技股份有限公司 | Cationic organosilicon polymer, microemulsion and preparation method thereof |
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| CN101338520A (en) * | 2008-07-11 | 2009-01-07 | 东莞市德能化工有限公司 | Organosilicon composite multifunction spinning dressing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101338520A (en) * | 2008-07-11 | 2009-01-07 | 东莞市德能化工有限公司 | Organosilicon composite multifunction spinning dressing agent |
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| CN105949468A (en) * | 2016-06-23 | 2016-09-21 | 杭州传化精细化工有限公司 | Preparation method for anionic linear copolymerized organic silicon softening and finishing agent |
| CN105949468B (en) * | 2016-06-23 | 2018-09-18 | 杭州传化精细化工有限公司 | A kind of anionic is linearly copolymerized the preparation method of organosilicon flexible finishing agent |
| CN106397776A (en) * | 2016-08-30 | 2017-02-15 | 浙江科峰有机硅有限公司 | Double amino type block polyether amino silicone oil and preparation method thereof |
| CN108951154A (en) * | 2018-05-23 | 2018-12-07 | 绍兴柯桥德美精细化工有限公司 | A kind of environment-friendly type terylene soft fabric, water repellent, anti-static multifunctional method for sorting |
| CN109280173A (en) * | 2018-09-13 | 2019-01-29 | 浙江润禾有机硅新材料有限公司 | A kind of super soft hydrophilic silicone oil and preparation method thereof |
| CN111171267A (en) * | 2020-01-20 | 2020-05-19 | 宁波润禾高新材料科技股份有限公司 | High-elasticity resin modified silicone oil and preparation method thereof |
| CN111171267B (en) * | 2020-01-20 | 2022-05-31 | 宁波润禾高新材料科技股份有限公司 | High-elasticity resin modified silicone oil and preparation method thereof |
| CN114230797A (en) * | 2021-12-30 | 2022-03-25 | 江苏奥斯佳材料科技股份有限公司 | Cationic organosilicon polymer, microemulsion and preparation method thereof |
| CN114230797B (en) * | 2021-12-30 | 2023-12-01 | 江苏奥斯佳材料科技股份有限公司 | Cationic organosilicon polymer, microemulsion and preparation method thereof |
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