CN102644200B - Super-soft finishing agent of silicone oil - Google Patents
Super-soft finishing agent of silicone oil Download PDFInfo
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- CN102644200B CN102644200B CN201210134513.2A CN201210134513A CN102644200B CN 102644200 B CN102644200 B CN 102644200B CN 201210134513 A CN201210134513 A CN 201210134513A CN 102644200 B CN102644200 B CN 102644200B
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Abstract
The invention relates to the textile finishing agent field, in particular to a super-soft finishing agent of silicone oil. The super soft finishing agent of the silicone oil comprises a silicone oil compound with the following cation structural formula as followed. The silicone oil compound occupies a weight percentage of 2%-60% in the finishing agent, n1 is 5-10, R is a polyether group, and a polymerization degree is 3-50. The super soft finishing agent of the silicone oil is suitable for feel finishing of one or more fiber constituted fabric such as cotton, Dacron, chinlon and acrylic fibers, and provided with better soft, smooth and fluffy effects than amino-modified silicone oil and excellent stability in resistance to acid and alkali, electrolyte, high temperature, shearing and the like; and problems of easy demulsification, floating oil, roll banding, difficult rework and the like in the existing amino-modified silicone oil are completely solved.
Description
Technical field
The present invention relates to textile finish field, relate in particular to a kind of super soft sillicon oil treatment agent.
Background technology
In the hand feel finishing agent of textiles, more than 80% need to use amido silicon oil in the market.Amido silicon oil is that grow up the eighties in last century a kind of is mainly used in softness, the modified silicon oil that fluffy, smooth hand arranges, its molecular backbone chain is that the Si-O key with excellent flexibility forms, on side chain, according to different amino silicane coupling agents, introduced the amino of different structure, amino has the chemical propertys such as stronger polarity, reactivity, adsorptivity, thereby has given amido silicon oil geneogenous advantage on fabric feeling finishing effect.But amido silicon oil can not directly be used, must add after emulsifying agent is emulsified into emulsion and could use.Through technical development for many years, the selection of amino silicone oil emulsifying agent, the aspects such as optimization of emulsifying process have obtained changing thoroughly, but still can not be from solve in essence amido silicon oil use procedure easily breakdown of emulsion, floating oil, roll banding, sticky cylinder, easily produce the problems such as silicone oil spot, meanwhile, the introducing of the highly active amino of side chain has caused fabric after the easy look change of fabric, xanthochromia, the processing a series of problem such as 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 the raw material dependence on import due to synthetic operation more complicated, key, particularly can not 100% in the addition process of silicon hydrogen and glycidyl allyl ether transform, cause that block silicone oil quality is in the market 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, cannot embody the effect that amido silicon oil has; In synthetic process, adopted a large amount of volatile solvents simultaneously, although harmless, rear arrangement processing environment has been brought to 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 the preparation of the amidation of amino coupling agent, the preparation of holding hydrogeneous methylsiloxane intermediate, polysiloxane-polyether linear block copolymers and four preparation processes such as ammonia solution of segmented copolymer, whole building-up process relates to a plurality of heterogeneous chemical reactions, stability influence to product quality is larger, in the multiple conversion of amino, affected amino activity, its treatment effect is significantly declined.
Publication number is the preparation method that the patent of invention of CN101497697A discloses a kind of polysiloxanes-amidopolyether block copolymer, method has comprised α, the preparation of ω-hydrogen siloxane intermediate, α, the preparation of ω-bicyclic oxygen polysiloxane intermediate, three steps of preparation of polysiloxanes-amidopolyether block copolymer, 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 polysiloxane intermediate, epoxy group(ing) is at high temperature, under acid condition, easily open loop has a strong impact on follow-up synthesizing, and then affect the quality stability of product.In polysiloxanes-amidopolyether block copolymer building-up process, adopted Amino Terminated polyether(ATPE), Amino Terminated polyether(ATPE) is mainly controlled by U.S. Huntsman Corporation at present, product price is higher, of less types, cause that the product cost produced is higher, the scope of application is narrower, be mainly used in trevira hand feel finishing and on other fiber treatment effect 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 super soft sillicon oil treatment agent.The super soft sillicon oil treatment agent of the present invention is applicable to the hand feel finishing of one or more fibrous fabrics of cotton, terylene, polyamide fibre, acrylic fibers, there is soft, sliding, the fluffy effect that surmounts amido silicon oil, have more excellent acid and alkali-resistance, electrolyte-resistant, high temperature resistant, resistance to shearing equistability, the 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 above-mentioned object, the present invention has adopted following technical scheme:
A super soft sillicon oil treatment agent, this sillicon oil treatment agent comprises the silicon oil compound with following cationic structural formula, the weight ratio that described silicon oil compound accounts for finishing composition is 2% ~ 60%:
；
Described n1 is 5 ~ 10, and described R is polyethers group, and the polymerization degree is 3 ~ 50.
As preferably, described R is
, a=0 ~ 3 wherein, b=0 ~ 3, n=10 ~ 40.
As preferably, described negatively charged ion is one or several combination of sulfate ion, halo acid ion and aromatic sulfonic acid root.
The present invention, owing to having adopted above-mentioned technical scheme, has the following advantages with respect to prior art:
1) the sillicon oil treatment agent that prepared by the present invention adopts and domesticly easily produces, easily buying, end epoxidized polyether various in style are basic material, on the backbone structure of polysiloxane, successfully embed the polyether segment with excellent wetting ability, kindliness, product has excellent automatic emulsifying performance, hydrophilicity and materialization stability, has thoroughly solved the easy breakdown of emulsion of traditional amido silicon oil, floating oil, roll banding, sticky cylinder, easily produces oil mark, the problem such as be difficult for returning something for repairs;
2) the sillicon oil treatment agent that prepared by the present invention has been carried out alkylated cation modification on the basis of the organopolysiloxane polyether block copolymer of polysiloxane, amino, polyethers ternary block, polarity, adsorptivity and the reactivity of product under the condition of less amino content, have further been improved, can reduce significantly the consumption of finishing composition, and expanded the scope of application of product, various fibers are all had to excellent finishing effect, solved current block silicone oil in wool, cotton, the poor problem of acrylic fabric feel; The raising of cationization degree, gives super soft hydrophilic block silicone oil certain antibacterial, anti-static function, and the while can be given the fluffy feel as the distinguished eider down of fabric; Reactive hydrogen on amino is thoroughly replaced by alkylated reaction, efficiently solves the problem of easy xanthochromia under amino hot conditions, still less look change of fabric, xanthochromia after processing.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the scope of protection of present invention is not limited to the scope of embodiment statement.
embodiment 1-1 α, the preparation of omega-amino-polysiloxane intermediate
In the 2000ml there-necked flask of constant speed electric mixer, thermometer is housed, add 1,1,3 of the octamethylcyclotetrasiloxane (D4) of 1230g and 50 grams, 3-tetramethyl-two aminopropyl sily oxide, stir and are warmed up to 90-95 ℃ of left and right, then add 1.28g(CH
3)
4nOH content is 10% (CH
3)
4nOH alkali glue, insulation reaction 6 hours, after insulation finishes, is warmed up to 135 ℃, is incubated 1 hour, by catalyzer (CH
3)
4nOH fully decomposes, and slowly vacuumizes, and has a large amount of low-boiling-point substances to flow out, and in temperature, is 150 ℃, and relative vacuum degree be-condition of 99.9KPa, pull out low-boiling-point substance 1 hour, until there is no material outflow.Synthetic product is colorless transparent viscous liquid, and ammonia value is: 0.345mmol/g, viscosity is: 50-55cs, fugitive constituent is :≤1%.
embodiment 1-2 α, ω--the preparation of amino silicones intermediate
In the 2000ml there-necked flask of constant speed electric mixer, thermometer is housed, add 1,1,3 of the octamethylcyclotetrasiloxane (D4) of 1640g and 50 grams, 3-tetramethyl-two aminopropyl sily oxide, stir and are warmed up to 90-95 ℃ of left and right, then add 1.7g(CH
3)
4nOH content is 10% (CH
3)
4nOH alkali glue, insulation reaction 6 hours, after insulation finishes, is warmed up to 135 ℃, is incubated 1 hour, by catalyzer (CH
3)
4nOH fully decomposes, and slowly vacuumizes, and has a large amount of low-boiling-point substances to flow out, and in temperature, is 150 ℃, and relative vacuum degree be-condition of 99.9KPa, pull out low-boiling-point substance 1 hour, until there is no material outflow.Synthetic product is colorless transparent viscous liquid, and ammonia value is: 0.26mmol/g, viscosity is: 100-110cs, fugitive constituent is :≤1%.
embodiment 2-1 end epoxidized polyether and α, the preparation of omega-amino-polysiloxane intermediate block polymerization
Constant speed electric mixer is being housed, in the 2000ml there-necked flask of thermometer, the α that adds 800g embodiment 1-1 to prepare, omega-amino-polysiloxane intermediate, (the pfpe molecule amount of end epoxidized polyether is 920 to the end epoxidized polyether of 106g, a+b=3, n=14), the ethylene glycol monobutyl ether of 604g, open and stir, fully stir after 30 minutes, slowly be warmed up to 80-85 ℃ of left and right, insulation reaction 20 hours, can obtain transparent flaxen polysiloxane, amino, the organopolysiloxane polyether block copolymer of polyethers ternary block, viscosity is 500-550cs, solid content is 60 ± 1%.
embodiment 2-2 end epoxidized polyether and α, the preparation of omega-amino-polysiloxane intermediate block polymerization
Constant speed electric mixer is being housed, in the 2000ml there-necked flask of thermometer, the α that adds 800g embodiment 1-1 to prepare, omega-amino-polysiloxane intermediate, (the pfpe molecule amount of end epoxidized polyether is 1850 to the end epoxidized polyether of 214g, a+b=3, n=34-36), the ethylene glycol monobutyl ether of 676g, open and stir, fully stir after 30 minutes, slowly be warmed up to 80-85 ℃ of left and right, insulation reaction 20 hours, can obtain transparent flaxen polysiloxane, amino, the organopolysiloxane polyether block copolymer of polyethers ternary block, viscosity is 600-650cs, solid content is 60 ± 1%.
embodiment 2-3 end epoxidized polyether and α, the preparation of omega-amino-polysiloxane intermediate block polymerization
Constant speed electric mixer is being housed, in the 2000ml there-necked flask of thermometer, the α that adds 800g embodiment 1-2 to prepare, omega-amino-polysiloxane intermediate, (the pfpe molecule amount of end epoxidized polyether is 920 to the end epoxidized polyether of 96g, a+b=3, n=14), the ethylene glycol monobutyl ether of 597g, open and stir, fully stir after 30 minutes, slowly be warmed up to 80-85 ℃ of left and right, insulation reaction 20 hours, can obtain transparent flaxen polysiloxane, amino, the organopolysiloxane polyether block copolymer of polyethers ternary block, viscosity is 800-850cs, solid content is 60 ± 1%.
embodiment 2-4 end epoxidized polyether and α, the preparation of omega-amino-polysiloxane intermediate block polymerization
Constant speed electric mixer is being housed, in the 2000ml there-necked flask of thermometer, the α that adds 800g embodiment 1-2 to prepare, omega-amino-polysiloxane intermediate, (the pfpe molecule amount of end epoxidized polyether is 1850 to the end epoxidized polyether of 193g, a+b=3, n=34-36), the ethylene glycol monobutyl ether of 662g, open and stir, fully stir after 30 minutes, slowly be warmed up to 80-85 ℃ of left and right, insulation reaction 20 hours, can obtain transparent flaxen polysiloxane, amino, the organopolysiloxane polyether block copolymer of polyethers ternary block, viscosity is 875-900cs, solid content is 60 ± 1%.
the cation-modified preparation of embodiment 3-1 organopolysiloxane polyether block copolymer
On the basis that completes embodiment 2-1, directly add the monochloroethane of 18g, after fully stirring, stir and be warmed up to 95-100 ℃ of left and right, insulation reaction 4 hours, get final product to obtain the super soft hydrophilic block silicone oil of faint yellow transparent viscous fluid, viscosity is 600cs, and solid content is 60 ± 1%.
the cation-modified preparation of embodiment 3-2 organopolysiloxane polyether block copolymer
On the basis that completes embodiment 2-2, directly add the monochloroethane of 18g, after fully stirring, stir and be warmed up to 95-100 ℃ of left and right, insulation reaction 4 hours, get final product to obtain the super soft hydrophilic block silicone oil of faint yellow transparent viscous fluid, viscosity is 715cs, and solid content is 60 ± 1%.
the cation-modified preparation of embodiment 3-3 organopolysiloxane polyether block copolymer
On the basis that completes embodiment 2-3, directly add the monochloroethane of 13.5g, after fully stirring, stir and be warmed up to 95-100 ℃ of left and right, insulation reaction 4 hours, get final product to obtain the super soft hydrophilic block silicone oil of faint yellow transparent viscous fluid, viscosity is 905cs, and solid content is 60 ± 1%.
the cation-modified preparation of embodiment 3-4 organopolysiloxane polyether block copolymer
On the basis that completes embodiment 2-4, directly add the monochloroethane of 13.5g, after fully stirring, stir and be warmed up to 95-100 ℃ of left and right, insulation reaction 4 hours, get final product to obtain the super soft hydrophilic block silicone oil of faint yellow transparent viscous fluid, viscosity is 1000cs, and solid content is 60 ± 1%.
To above-described embodiment 3-X(X=1-4) product of producing carries out the detection of the contrast of effect and physics, chemical stability:
1, the preparation of finishing composition
Get above-described embodiment 3-X(X=1-4) the prepared content product 100g that is 60%, while stirring, slowly add water, the amount of water is 500g, opens the emulsion of the zona pellucida blue light that rare one-tenth content is 10% left and right, finally add 2g Glacial acetic acid, pH value is adjusted between 5-6.
2, the application art of finishing composition
Process fabric: cotton bleaching Woven Fabrics, T/C bleach looped fabric, entirely wash and bleach looped fabric, terylene lint
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.
The contrast of 3.1 feels
The effect of the processing fabric of softening agent feels that by the mode touching with hand the composite factors such as loft after fabric treating, pliability, rebound resilience and smooth degree evaluate, feel is divided into 5 each grades, rank is more high better, 5 grades best, 1 grade minimum, and in table 1, feel level data has evaluating and draw with hand touch of experience technician by five.
3.2 hydrophilic contrasts
With standard dropper, from the fabric face of sprawling to level from fabric 10cm At The Height, drip 1 and drip, measure 1 and drip complete wetting, diffusion, infiltration time used on fabric face from quiescent conditions, the time used is shorter, illustrates that its hydrophilic effect is better.
The mensuration of 3.3 xanthochromias
Bleached woven fabric (former cloth) before not processing through finishing composition is measured the whiteness of fabric face by whiteness instrument, fabric is measured the whiteness of fabric face after finishing composition is processed sizing by whiteness instrument, by the contrast of two whiteness values, carry out the xanthochromia of evaluation agent, value difference is less, and the yellowing resistance of finishing composition can be better.
Table 1 result of use comparative evaluation
4, the detection of physics, chemical stability
The evaluation of table 2 stability
Ratings data by table 1, table 2 can be found out, adopt the synthetic super soft hydrophilic block silicone oil of end epoxidized polyether to process and on fabric, there is excellent soft right, fluffy, smooth feel, give fabric certain hydrophilicity simultaneously, on bleached woven fabric, substantially do not affect especially the whiteness of fabric; Aspect stability, there is excellent heat-resisting, resistance to shearing, acidproof, alkaline-resisting, salt tolerant, resistance to hard water stability, have a wide range of applications field and wide application prospect, can be thoroughly substituted-amino silicone oil comprehensively.
Claims (2)
1. a super soft sillicon oil treatment agent, is characterized in that: this sillicon oil treatment agent comprises the silicon oil compound with following cationic structural formula, and the weight ratio that described silicon oil compound accounts for finishing composition is 2% ~ 60%:
；
Described n1 is 5 ~ 10,
Described R is
, a=0 ~ 3 wherein, b=0 ~ 3, n=10 ~ 40.
2. a kind of super soft sillicon oil treatment agent according to claim 1, is characterized in that: negatively charged ion is one or several combination of sulfate ion, halo acid ion and aromatic sulfonic acid root.
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| CN105155280B (en) * | 2015-10-10 | 2016-05-04 | 珠海华大浩宏化工有限公司 | A kind of ice sense finishing agent and preparation method thereof |
| CN105696335A (en) * | 2016-03-11 | 2016-06-22 | 湖州宏鑫绸厂 | Acid-resisting finishing method for viscose fabric |
| CN107815860A (en) * | 2017-11-13 | 2018-03-20 | 鹤山弘扬制衣有限公司 | The production method of tweed |
| CN107780208A (en) * | 2017-11-13 | 2018-03-09 | 鹤山弘扬制衣有限公司 | The processing method of tweed |
| CN111434846A (en) * | 2019-01-15 | 2020-07-21 | 东丽纤维研究所（中国）有限公司 | Soft fabric |
| CN112127164A (en) * | 2020-09-17 | 2020-12-25 | 河南瑞贝卡发制品股份有限公司 | Preparation and impregnation method of post-finishing soft-keeping agent for synthetic fibers |
| CN112853762A (en) * | 2021-02-20 | 2021-05-28 | 诸暨九丰纺织科技有限公司 | Novel fluffy soft polyester fabric finishing agent and production process thereof |
| CN115058013B (en) * | 2022-08-17 | 2022-11-22 | 江苏奥斯佳材料科技股份有限公司 | Organic silicon polymer and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102250358A (en) * | 2011-05-18 | 2011-11-23 | 黄山市强力化工有限公司 | Block type amino polyether modified silicone oil and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102250358A (en) * | 2011-05-18 | 2011-11-23 | 黄山市强力化工有限公司 | Block type amino polyether modified silicone oil and preparation method thereof |
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Effective date of registration: 20191115 Address after: No. 168, Jinhai Middle Road, Binhai New Area, South Ningbo, Ninghai County, Ningbo City, Zhejiang Province Patentee after: Ningbo run Wo hi tech materials Polytron Technologies Inc Address before: 313200, 102, Albert Road, Changhong East Street, Deqing County Economic Development Zone, Zhejiang, Huzhou Patentee before: Zhejiang Runhe Organic Silicon New Material Co., Ltd. |
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