CN112962314B - Multi-arm associated polyurethane composite modified organic silicon softener emulsion and preparation method thereof - Google Patents
Multi-arm associated polyurethane composite modified organic silicon softener emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of polyurethane modified organosilicon softener emulsion for finishing various textile hand feeling styles, and discloses a preparation method of multi-arm associated polyurethane composite modified organosilicon softener emulsion. The method comprises the following steps: preparing raw materials; dewatering pretreatment; primary end sealing; secondary end capping; mixing and emulsifying. Various macromolecules in the softener emulsion prepared by the method can be effectively associated with each other, and the blending modification of the traditional organosilicon softener on textile fibers is realized in an intermolecular entanglement manner. The self-made polyurethane modified polysiloxane polymer has three long-chain branched arms with different structures, and a plurality of multi-arm structure molecules have certain series connection. Compared with the traditional organosilicon softener, the softener emulsion can endow various textiles with obviously better hydrophilicity and high elastic hand feeling; the product has low emulsifier content, safety, environmental protection, convenient use and good market prospect.
Description
Technical Field
The invention relates to the field of polyurethane modified (resin type) organosilicon softener emulsion for finishing hand feeling styles of various textiles, in particular to a preparation method of multi-arm associated polyurethane composite modified organosilicon softener emulsion.
Background
In the last 10 years, as textile chemicals which are most widely applied, most used and most abundant in variety in textile printing and dyeing processing, the organosilicon softener has developed bottlenecks in monomer polymerization, preparation technology and style characteristics. In order to seek breakthrough, related science and technology personnel continuously try to introduce a non-silicon high polymer material with excellent characteristics into an organic silicon softener structure or a formula system so as to obtain brand-new or rich and varied textile characteristic styles such as hydrophilicity, high elasticity, fullness, fineness, softness and glutinous property. In view of the excellent adhesion, elasticity, skin feel and designability of structure of the waterborne polyurethane, the relevant research and development work is focused on the composite modification of the silicone emulsion and the polyurethane. However, the aqueous polyurethane lacks a common structure with the silicone softener, and the polarity difference between the aqueous polyurethane and the silicone softener is great, so that the aqueous polyurethane and the silicone softener have incompatibility and poor compatibility in terms of chemical structures, so that the positive contribution of the polyurethane to the style effect of the silicone softener is not obvious and uncertain, and the purpose of blending modification cannot be achieved at all.
Therefore, the polysiloxane and the polyurethane are combined by a chemical means, the chemical and supermolecular structure of the hybrid high polymer are designed in a targeted manner, the compatibility of the hybrid high polymer and the organic silicon softener is improved, a brand new hand feeling style is obtained from the chemical structure and the supermolecular structure of the product, and the hybrid high polymer is a main direction for the development of the composite modified organic silicon softener product.
At present, the physical and chemical modification technical scheme of the organic silicon softener mainly comprises the following steps:
1. the polyether polyurethane block organosilicon softening agent is prepared with the material including polymerized monomer, modified monomer, assistant and solvent, and has the material composition: the polymeric monomer comprises diisocyanate, polyethylene glycol and cyclosiloxane; the modified monomer is fatty amine and an organic silicon end capping agent; the adjuvant is a polymerization catalyst; the solvent is isopropanol, acetone and deionized water.
For example, the preparation method of polyether urethane block organosilicon softening agent disclosed in "synthesis of block type urethane modified organosilicon softening agent" by shochu shogao, heijiang, minxin (university of sienna university of engineering, proceedings 2015 29 vol. 3) comprises the following steps: the polymerization monomer is isophorone diisocyanate, polyethylene glycol 2000, octamethylcyclotetrasiloxane; the modified monomer is n-butylamine and an organosilicon epoxy end-capping agent; the auxiliary agents are dibutyltin dilaurate and tetramethylammonium hydroxide.
The method provides a method for improving the organosilicon softener aiming at the defects of poor water solubility, easy yellowing and the like of the prior amino silicone oil. The self-made block type polyurethane modified organic silicon softener is superior to the commercial ternary block silicone oil in fabric softness, rebound resilience, hydrophilicity and whiteness. However, the polyurethane type silicone softener polymer with such a structure is a typical linear block structure, the primary chemical structure and the secondary supramolecular structure of the polymer are simple and lack of change, and two ends of a flexible polysiloxane chain link are subjected to the fixing effect of chemical bonds, so that the degree of freedom is poor, and the modification of the traditional silicone softener cannot be realized in a mode of 'forced intermolecular mutual dissolution (molecular entanglement)' through physical blending, and a positive modification effect is obtained.
2. The material includes bulk polymer, modified polymer, assistant and solvent, wherein: the main polymer and the modified polymer are amino silicone oil; the modified macromolecule is organic silicon elastomer; the auxiliary agent is polymerization catalyst, solvent, neutralizer and emulsifier.
The preparation method of the high-elasticity modified organosilicon softener disclosed by synthesis and application of organosilicon elastomer fabric finishing agent (9 th year 2017) of Guo Xiao, anqifeng and Li Xiaolu, which comprises the following steps: the polymer of the body and the high molecule of the modified substance are traditional amino silicone oil; the modified high-molecular organosilicon elastomer is prepared from side-chain hydrogen-containing silicone oil and vinyl-terminated silicone oil; the auxiliary agents are polymerization catalyst chloroplatinic acid, solvent isopropanol, emulsifier nonionic surfactant and neutralizer acetic acid.
According to the method, side chain hydrogen-containing silicone oil (PHMS) and vinyl-terminated silicone oil (VPS) are used as raw materials to prepare a Solid Silicone Elastomer (SSE), and the SSE is emulsified and dispersed in Amino Silicone Oil (ASO) to obtain a silicone elastomer fabric finishing agent, so that the fabric can be endowed with soft and smooth handfeel, and meanwhile, the emulsibility and water solubility of silicone resin are improved, and the application range of the silicone resin in fabric finishing is enlarged. However, the technical solution mainly pursues the elasticity, water repellency and softness of the finished fabric, and the technical measure is to blend the silicone elastomer with higher crosslinking degree in the traditional amino silicone oil. Because the non-silicon long-chain structure is not introduced in the technical scheme, the hand feeling style of the product still does not deviate from the basic characteristics of the organic silicon softening agent. Certainly, the modified silicone soft rubber is blended with the traditional silicone softening agent for modification, and has no novel and changeable hand feeling style characteristics.
3. The polyether polyurethane block organosilicon softening agent is prepared with the material including polymerized monomer, modified monomer and assistant, and has the material composition: the polymerization monomer comprises diisocyanate, polyethylene glycol, cyclosiloxane and bifunctional chain extender; the modified monomer is bifunctional fatty amine and an organosilicon end-capping agent; the adjuvant is a polymerization catalyst.
For example, a method for producing a polyether urethane block silicone softener, which is disclosed in "research on synthesis of silicone-urethane copolymer softener" by von na, heighuang, huxianhua et al (polyurethane industry 2016, volume 31, phase 3), comprises: the polymerization monomer is isophorone diisocyanate, polyethylene glycol 2000, octamethylcyclotetrasiloxane, micromolecular diol or diamine (1, 4-butanediol, ethylene glycol, ethylenediamine, diethanolamine/diethylenetriamine); the modified monomer is di-n-butylamine and an organosilicon epoxy end-capping reagent; the auxiliary agents are catalyst dibutyl tin dilaurate and tetramethyl ammonium hydroxide.
According to the method, hydroxyl-terminated silicone oil is adopted to modify polyurethane, hydrophilic polyether polyol and the hydroxyl-terminated silicone oil are connected together through aliphatic diisocyanate to prepare an organic silicon-polyurethane copolymer softening agent, and the softening performance and breaking strength of the fabric finished by the softening agent are improved. However, the polyurethane type silicone softener polymer with such a structure is a typical linear block structure, the primary chemical structure and the secondary supramolecular structure of the polyurethane type silicone softener polymer are simple and lack of change, and the two ends of the flexible polysiloxane chain link are subjected to the fixing action of chemical bonds, so that the degree of freedom is poor, and the modification of the traditional silicone softener cannot be realized in a mode of 'forced mutual dissolution between molecules (molecular entanglement)' through physical blending, and a positive modification effect is obtained.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a multi-arm associated polyurethane composite modified organosilicon softener emulsion and a preparation method thereof. The softening agent emulsion prepared by the invention has novel structure and obvious effect, and can be used for finishing the high-elastic soft style of various textiles. Various macromolecules in the multi-arm association type polyurethane composite modified organic silicon softener composite emulsion can be effectively associated with each other, and the blending modification of the traditional organic silicon softener is realized on textile fibers in an intermolecular entanglement mode. The self-made polyurethane modified polysiloxane polymer has three long-chain branched arms with different structures, and a plurality of multi-arm structure molecules have certain series connection. Compared with the traditional organic silicon softening agent, the product of the invention can endow various textiles with better hydrophilicity, especially outstanding elastic hand feeling; the product has low emulsifier content, safety, environmental protection, convenient use and good market prospect.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a multi-arm associative polyurethane composite modified silicone softener emulsion, comprising the following steps:
(1) Preparing raw materials: the raw materials contain a polymerization monomer, an auxiliary agent, an organic silicon softening agent and water; wherein the polymeric monomer comprises diisocyanate, hydroxyl-terminated polyether triol, hydroxyl-terminated polysiloxane and hydroxyl-terminated polyether diol; the auxiliary agents comprise a polymerization catalyst, a diluent, a neutralizer and an emulsifier; the organosilicon softener is amino silicone oil; the water is soft water;
the diisocyanate is isophorone diisocyanate;
the hydroxyl-terminated polyether triol is a random copolymer of ethylene oxide and propylene oxide with the molecular weight of 2000-4000;
the hydroxyl-terminated polysiloxane is bishydroxyalkyl polymethylsilane with the molecular weight of 2000-4000;
the hydroxyl-terminated polyether glycol is polyethylene glycol with the molecular weight of 2000-3000;
the polymerization catalyst is stannous octoate or dibutyltin dilaurate;
the diluent is one or a mixture of two of acetone, butanone and ethyl pyrrolidone;
the neutralizer is acetic acid;
the emulsifier is one or a mixture of two of isomeric alcohol ether nonionic emulsifiers;
the molar parts of the components in the polymerization monomer are as follows: 3.0 parts of diisocyanate, 1.0 part of hydroxyl-terminated polyether triol, 1.5-2.0 parts of hydroxyl-terminated polysiloxane and 1.0-1.5 parts of hydroxyl-terminated polyether diol, wherein the sum of the mole parts of the hydroxyl-terminated polysiloxane and the hydroxyl-terminated polyether diol is 2.7-3.1 parts;
the dosage of the polymerization catalyst is 0.06-0.08 wt% of the total weight of the polymerization monomers;
the dosage of the diluent is 80 to 90 weight percent of the total weight of the polymerized monomers;
the dosage of the neutralizer is 0.3-0.6 wt% of the weight of the amino silicone oil;
the dosage of the emulsifier is 6-12 wt% of the weight of the amino silicone oil;
the dosage of the amino silicone oil is 2 to 6 times of the total weight of the polymerized monomers;
the amount of water is adjusted to ensure that the solid content of the prepared multi-arm associated polyurethane composite modified organosilicon softener emulsion is 20-30%;
(2) Dewatering pretreatment: respectively carrying out dehydration pretreatment on hydroxyl-terminated polyether triol and hydroxyl-terminated polyether glycol under vacuum and heating conditions for later use;
(3) Primary end capping: carrying out primary end capping reaction on diisocyanate, hydroxyl-terminated polyether triol, a part of polymerization catalyst and a part of diluent to prepare a multi-arm associated polyurethane composite modified organosilicon softener intermediate;
(4) Secondary end capping: carrying out secondary end capping reaction on the multi-arm associative polyurethane composite modified organic silicon softener intermediate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether glycol, the rest of polymerization catalyst and the rest of diluent to prepare multi-arm associative polyurethane composite modified organic silicon softener macromolecules;
(5) Mixing and emulsifying: mixing and emulsifying the multi-arm associative polyurethane composite modified organic silicon softener macromolecule, the neutralizer, the emulsifier, the water and the organic silicon softener to prepare the multi-arm associative polyurethane composite modified organic silicon softener emulsion.
Preferably, the step (2) is specifically:
(2.1) respectively putting hydroxyl-terminated polyether triol and hydroxyl-terminated polyether diol into different reactors;
(2.2) treating at 105-110 ℃ and-0.100-0.098 MPa vacuum degree for 70-80 min respectively for later use.
Preferably, the step (3) is specifically:
(3.1) adding diisocyanate into a reactor, adding 50-70% of the hydroxyl-terminated polyether triol obtained in the step (2) within 40-60 min at 70-80 ℃, and then carrying out heat preservation reaction for 20-30 min;
(3.2) maintaining the reaction temperature at 70-80 ℃, adding the rest of the hydroxyl-terminated polyether triol obtained in the step (2), and then carrying out heat preservation reaction for 20-30 min;
(3.3) adding 40-60% of diluent and 40-60% of polymerization catalyst into (3.2), and reacting for 20-30 min at the temperature of 75-85 ℃;
(3.4) heating to 86-90 ℃, and reacting for 60-90 min under the condition of heat preservation; cooling to 77-83 ℃, and then carrying out heat preservation reaction for 20-30 min to obtain the multi-arm associated polyurethane composite modified organosilicon softener intermediate.
Preferably, the step (4) is specifically:
(4.1) putting the hydroxyl-terminated polyether glycol obtained in the step (2), hydroxyl-terminated polysiloxane and the rest of diluent into a reactor, and uniformly mixing;
(4.2) adding the multi-arm associated polyurethane composite modified organosilicon softener intermediate obtained in the step (3) within 30-40 min at 80-85 ℃, and then carrying out heat preservation reaction for 30-40 min;
(4.3) adding the residual catalyst, and continuing to react for 90-120 min at the temperature of 80-85 ℃ to prepare the multi-arm associated polyurethane composite modified organosilicon softener polymer.
Preferably, the step (5) is specifically:
(5.1) cooling the material obtained in the step (4) to 35-45 ℃;
(5.2) adding an emulsifier, a neutralizer and an organic silicon softening agent, fully mixing and maintaining stirring for neutralization for 20-30 min;
(5.3) adding water, stirring at a high speed, emulsifying uniformly, and keeping stirring for 20-30 min;
and (5.4) standing and defoaming to prepare the multi-arm associated polyurethane composite modified organosilicon softener emulsion.
Preferably, the amino silicone oil is amino silicone oil with an ammonia value of 0.3-0.6 and a solid content of 60-80%.
Preferably, the water is soft water having a total hardness of less than 5 degrees.
Preferably, the diluent is used in an amount of 80.5 to 88 wt% based on the total weight of the polymerized monomers.
Preferably, the emulsifier is used in an amount of 8 to 10 wt% based on the weight of the amino silicone oil.
The second aspect of the invention provides the multi-arm associated polyurethane composite modified organosilicon softener emulsion prepared by the method.
Compared with the prior art, the invention has the following advantages and characteristics:
1. in the invention, in order to seek a stable 'forced mutual solubility' structure formed by the product and the traditional organic silicon softener polymer, the nonlinear polymer structure and the distribution thereof are designed in a targeted way. Namely: according to the concept of 'innovation of chemical and physical structures', the organic silicon chain link, the polyether chain link and the nonionic aqueous polyurethane chain link are combined with each other in a specially designed position relationship, and the technical measures of 'starvation feeding and continuous polymerization' are adopted, so that the multi-arm organic silicon modified polyurethane structure is realized, and a novel style effect is obtained.
2. In the invention, based on the chemical and supermolecular structure design of polyurethane and polysiloxane nonlinear multi-hybrid macromolecules and through reaction control, the chemical structure (chain link, structure distribution) and supermolecular structure (branched multi-arm, star-linked) design of organosilicon/polyurethane/polyether nonlinear hybrid macromolecules are realized. The self-made polyurethane modified polysiloxane polymer has a branched multi-arm long-chain + long-chain star-linked structure consisting of polyethylene glycol and polysiloxane, and can form a stable forced mutual-solubility structure with the traditional organic silicon softener polymer, so that the application properties (high elasticity, hydrophilicity and the like) of the product are guaranteed. Actually, according to the formula and the design of a polymerization process, the self-made polyurethane modified polysiloxane polymer has three long-chain branched arms with different structures, and a plurality of multi-arm structure molecules have certain series connection, so that the polyurethane modified polysiloxane polymer is beneficial to forming a stable intermolecular entangled structure with the traditional organic silicon softener polymer, and a remarkable modification effect is favorably obtained.
3. In the invention, based on the chemical and special supermolecular structural design of polyurethane and polysiloxane nonlinear multi-hybrid high molecules, a product structural design and control method is researched, and the complex nonlinear (branched multi-arm + star-linked) multi-hybrid organic silicon modified polyurethane high molecules are realized through reaction conditions and control thereof, monomer proportioning design, feeding sequence design, charging speed design and the like.
4. In the invention, the obtained product and various polysiloxane (organosilicon) softeners can form a sufficient intermolecular entangled structure, the two have good compatibility and compatibility, and a polyurethane structure and a functional structure (different branched arms) can be effectively introduced into a softener composite system through the product. Compared with the traditional organic silicon softening agent, the product of the invention can endow various textiles with obviously better hydrophilicity and high elastic hand feeling.
5. In the invention, the multi-arm polyether type organic silicon modified polyurethane (similar to a polyurethane surfactant) is used as the emulsifier of the amino silicone oil, so that the purpose of compound modification of the amino silicone oil is realized, the use of the emulsifier is greatly reduced, and the multi-arm polyether type organic silicon modified polyurethane is safe, environment-friendly and convenient to use and has good market prospect.
6. In the invention, the product and the traditional organic silicon softener macromolecule are combined with each other in a mode of forming a forced interpenetrating network on a molecular level, thereby effectively inhibiting the mutual separation of the product and the traditional organic silicon softener macromolecule in the heat treatment process; meanwhile, the product has the application performance characteristics brought by various chemical structures such as polysiloxane, polyurethane, polyether and the like, and the product has better compatibility with the organic silicon softener, so that the composite has rich hand feeling and obvious characteristics.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a preparation method of multi-arm associated polyurethane composite modified organosilicon softener emulsion, which comprises the following steps:
(1) Preparing raw materials: the raw materials contain a polymerization monomer, an auxiliary agent, an organic silicon softening agent and water; wherein the polymeric monomer comprises diisocyanate, hydroxyl-terminated polyether triol, hydroxyl-terminated polysiloxane and hydroxyl-terminated polyether diol; the auxiliary agents comprise a polymerization catalyst, a diluent, a neutralizer and an emulsifier; the organosilicon softener is amino silicone oil; the water is soft water;
the diisocyanate is isophorone diisocyanate;
the hydroxyl-terminated polyether triol is a random copolymer of ethylene oxide and propylene oxide with the molecular weight of 2000-4000;
the end hydroxyl alkyl polysiloxane is double-end hydroxyl alkyl polymethylsilane with the molecular weight of 2000-4000;
the hydroxyl-terminated polyether glycol is polyethylene glycol with the molecular weight of 2000-3000;
the polymerization catalyst is stannous octoate or dibutyltin dilaurate;
the diluent is one or a mixture of two of acetone, butanone and ethyl pyrrolidone;
the neutralizer is acetic acid;
the emulsifier is one or a mixture of two of isomeric alcohol ether nonionic emulsifiers;
the polymerized monomer comprises the following components in parts by mole: 3.0 parts of diisocyanate, 1.0 part of hydroxyl-terminated polyether triol, 1.5-2.0 parts of hydroxyl-terminated polysiloxane and 1.0-1.5 parts of hydroxyl-terminated polyether glycol, wherein the sum of the mole parts of the hydroxyl-terminated polysiloxane and the hydroxyl-terminated polyether glycol is 2.7-3.1;
the dosage of the polymerization catalyst is 0.06-0.08 wt% of the total weight of the polymerization monomers;
the dosage of the diluent is 80 to 90 weight percent of the total weight of the polymerized monomers;
the dosage of the neutralizer is 0.3-0.6 wt% of the weight of the amino silicone oil;
the dosage of the emulsifier is 6-12 wt% of the weight of the amino silicone oil;
the dosage of the amino silicone oil is 2 to 6 times of the total weight of the polymerized monomers;
the amount of water is adjusted to ensure that the solid content of the prepared multi-arm associated polyurethane composite modified organosilicon softener emulsion is 20-30%;
(2) Dewatering pretreatment: respectively carrying out dehydration pretreatment on hydroxyl-terminated polyether triol and hydroxyl-terminated polyether glycol under vacuum and heating conditions for later use;
(3) Primary end capping: carrying out primary end capping reaction on diisocyanate, hydroxyl-terminated polyether triol, partial polymerization catalyst and partial diluent to prepare a multi-arm associated polyurethane composite modified organosilicon softener intermediate;
(4) Secondary end capping: carrying out secondary end capping reaction on the multi-arm associative polyurethane composite modified organic silicon softener intermediate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether glycol, the rest of polymerization catalyst and the rest of diluent to prepare multi-arm associative polyurethane composite modified organic silicon softener macromolecules;
(5) Mixing and emulsifying: mixing and emulsifying the multi-arm associative polyurethane composite modified organosilicon softener macromolecule, a neutralizer, an emulsifier, water and an organosilicon softener to prepare the multi-arm associative polyurethane composite modified organosilicon softener emulsion.
In a specific embodiment, the polymerization catalyst may be used in an amount of 0.06 wt%, 0.062 wt%, 0.064 wt%, 0.066 wt%, 0.068 wt%, 0.07 wt%, 0.072 wt%, 0.074 wt%, 0.076 wt%, 0.078 wt%, 0.08 wt% based on the total weight of the polymerized monomers.
In particular embodiments, the neutralizing agent may be used in an amount of 0.3 wt.%, 0.35 wt.%, 0.4 wt.%, 0.45 wt.%, 0.5 wt.% based on the weight of the amino silicone oil. 0.55 wt% or 0.6 wt%.
In specific embodiments, the amino silicone oil is used in an amount of 2 times, 2.5 times, 3 times, 3.5 times, 4 times, 4.5 times, 5 times, 5.5 times, or 6 times the total weight of the polymerized monomers.
In a preferred embodiment, the step (2) is specifically:
(2.1) respectively putting hydroxyl-terminated polyether triol and hydroxyl-terminated polyether diol into different reactors;
(2.2) treating at 105-110 ℃ and-0.100-0.098 MPa vacuum degree for 70-80 min for later use.
In a preferred embodiment, the step (3) is specifically:
(3.1) adding diisocyanate into a reactor, adding 50-70% of the hydroxyl-terminated polyether triol obtained in the step (2) within 40-60 min at 70-80 ℃, and then carrying out heat preservation reaction for 20-30 min;
(3.2) maintaining the reaction temperature at 70-80 ℃, adding the rest of the hydroxyl-terminated polyether triol obtained in the step (2), and then carrying out heat preservation reaction for 20-30 min;
(3.3) adding 40-60% of diluent and 40-60% of polymerization catalyst into (3.2), and reacting for 20-30 min at 75-85 ℃;
(3.4) heating to 86-90 ℃, and reacting for 60-90 min under the condition of heat preservation; cooling to 77-83 ℃, and then carrying out heat preservation reaction for 20-30 min to obtain the multi-arm association type polyurethane composite modified organosilicon softener intermediate.
In the invention, in the step (3.1), the hydroxyl-terminated polyether triol is added slowly after being added for 40-60 min.
In a preferred embodiment, the step (4) is specifically:
(4.1) putting the hydroxyl-terminated polyether glycol obtained in the step (2), hydroxyl-terminated polysiloxane and the rest of diluent into a reactor, and uniformly mixing;
(4.2) adding the multi-arm associated polyurethane composite modified organosilicon softener intermediate obtained in the step (3) within 30-40 min at 80-85 ℃, and then carrying out heat preservation reaction for 30-40 min;
(4.3) adding the rest catalyst, and continuing to react for 90-120 min at the temperature of 80-85 ℃ to prepare the multi-arm association type polyurethane composite modified organosilicon softener polymer.
In particular embodiments, in step (4.3), the reaction time may be 90min, 95min, 100min, 105min, 110min, 115min, or 120min.
In the invention, in the step (4.2), the multi-arm association type polyurethane composite modified organosilicon softener intermediate is added within 30-40 min, which is a slow adding process.
In a preferred embodiment, the step (5) is specifically:
(5.1) cooling the material obtained in the step (4) to 35-45 ℃;
(5.2) adding an emulsifier, a neutralizer and an organic silicon softening agent, fully mixing and maintaining stirring for neutralization for 20-30 min;
(5.3) slowly and continuously adding water, stirring at a high speed, emulsifying uniformly, and then maintaining stirring for 20-30 min;
and (5.4) standing and defoaming to prepare the multi-arm associated polyurethane composite modified organosilicon softener emulsion.
In a preferred embodiment, the amino silicone oil has an ammonia value of 0.3 to 0.6 and a solid content of 60 to 80%. In a particular embodiment, the amino silicone oil may be a commercially available product.
In a preferred embodiment, the water is soft water having a total hardness of less than 5 degrees, that is to say a total hardness of less than 50ppm cao.
In a preferred embodiment, the diluent is used in an amount of 80.5 to 88 wt% based on the total weight of the polymerized monomers.
In particular embodiments, the diluent may be used in an amount of 80 wt%, 80.5 wt%, 81 wt%, 81.5 wt%, 82 wt%, 82.5 wt%, 83 wt%, 83.5 wt%, 84 wt%, 84.5 wt%, 85 wt%, 85.5 wt%, 86 wt%, 86.5 wt%, 87 wt%, 87.5 wt%, 88 wt%, 88.5 wt%, 89 wt%, 89.5 wt%, or 90 wt% based on the total weight of the polymerized monomers.
In a preferred embodiment, the emulsifier is used in an amount of 8 to 10% by weight based on the weight of the aminosilicone.
In particular embodiments, the emulsifier may be used in an amount of 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, or 12 weight percent based on the weight of the amino silicone oil.
The second aspect of the invention provides the multi-arm associated polyurethane composite modified organosilicon softener emulsion prepared by the method.
The softening agent emulsion prepared by the method can be used for finishing and processing the soft style of various textiles, and the product has the advantages of low emulsifier content, safety, environmental protection, convenient use and good market prospect. Can endow various textiles with obviously better hydrophilicity and elastic hand feeling, compared with the traditional amino modified organosilicon softener: the hydrophilicity of the finished cotton fabric can be shortened from 300-400 s to 20-40 s, and the fold recovery angle can be increased from about 10 degrees to 55-90 degrees. The finished product should be stored in a shady, cool and dry place in a sealed way.
The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereto.
TABLE 1
Example 1
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) Dewatering pretreatment: respectively carrying out dehydration pretreatment on hydroxyl-terminated polyether triol and hydroxyl-terminated polyether glycol under vacuum and heating conditions for later use;
(2.1) respectively putting hydroxyl-terminated polyether triol and hydroxyl-terminated polyether diol into different reactors;
(2.2) respectively treating at 102 deg.C and-0.099 MPa for 77 min;
(3) Primary end capping: carrying out primary end capping reaction on diisocyanate, hydroxyl-terminated polyether triol, a part of polymerization catalyst and a part of diluent to prepare a multi-arm associated polyurethane composite modified organosilicon softener intermediate;
(3.1) adding diisocyanate into a reactor, slowly adding 50% of hydroxyl-terminated polyether triol obtained in the step (2.2) within 57min at 72 ℃, and then carrying out heat preservation reaction for 22min;
(3.2) maintaining the reaction temperature at 72 ℃, adding the residual hydroxyl-terminated polyether triol obtained in the step (2.2) at one time, and then carrying out heat preservation reaction for 22min;
(3.3) adding 50% of diluent and 50% of polymerization catalyst into (3.2), and maintaining the temperature at 77 ℃ for reaction for 22min;
(3.4) heating to 88 ℃, and keeping the temperature to react for 70min; cooling to 80 ℃, and then carrying out heat preservation reaction for 22min to obtain a multi-arm association type polyurethane composite modified organic silicon softener intermediate;
(4) Secondary end capping: carrying out secondary end capping reaction on the multi-arm associative polyurethane composite modified organic silicon softener intermediate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether glycol, the rest of polymerization catalyst and the rest of diluent to prepare multi-arm associative polyurethane composite modified organic silicon softener macromolecules;
(4.1) putting the hydroxyl-terminated polyether glycol and hydroxyl-terminated alkyl polysiloxane in the step (2.2) and the rest of diluent into a reactor, and uniformly mixing;
(4.2) slowly adding the multi-arm association type polyurethane composite modified organosilicon softener intermediate in the step (3.4) within 37min at 82 ℃, and then carrying out heat preservation reaction for 37min;
(4.3) adding the residual catalyst, and continuing to react for 95min at 82 ℃ to prepare the multi-arm associated polyurethane composite modified organosilicon softener polymer;
(5) Mixing and emulsifying: mixing and emulsifying a multi-arm associative polyurethane composite modified organosilicon softener macromolecule, a neutralizer, an emulsifier, water and an organosilicon softener to prepare a multi-arm associative polyurethane composite modified organosilicon softener emulsion;
(5.1) cooling the material obtained in the step (4.3) to 40 ℃;
(5.2) adding an emulsifier, a neutralizer and a traditional commercial organosilicon softener, fully mixing, and keeping stirring and neutralizing for 25min;
(5.3) slowly and continuously adding water, stirring at a high speed, emulsifying uniformly, and keeping stirring for 25min;
and (5.4) standing and defoaming to prepare the multi-arm associated polyurethane composite modified organosilicon softener emulsion S1 (the solid content is 20.9%).
Example 2
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) Dewatering pretreatment: respectively carrying out dehydration pretreatment on hydroxyl-terminated polyether triol and hydroxyl-terminated polyether glycol under vacuum and heating conditions for later use;
(2.1) respectively putting hydroxyl-terminated polyether triol and hydroxyl-terminated polyether diol into different reactors;
(2.2) respectively treating at 108 deg.C and-0.098 MPa for 78 min;
(3) Primary end capping: carrying out primary end capping reaction on diisocyanate, hydroxyl-terminated polyether triol, partial polymerization catalyst and partial diluent to prepare a multi-arm associated polyurethane composite modified organosilicon softener intermediate;
(3.1) adding diisocyanate into a reactor, slowly adding 60% of hydroxyl-terminated polyether triol obtained in the step (2.2) within 50min at 75 ℃, and then carrying out heat preservation reaction for 27min;
(3.2) maintaining the reaction temperature at 75 ℃, adding the residual hydroxyl-terminated polyether triol obtained in the step (2.2) at one time, and then carrying out heat preservation reaction for 28min;
(3.3) adding 50% of diluent and 50% of polymerization catalyst into (3.2), and maintaining the temperature at 80 ℃ for reacting for 28min;
(3.4) heating to 88 ℃, and reacting for 80min under the condition of heat preservation; cooling to 80 ℃, and then carrying out heat preservation reaction for 22min to obtain a multi-arm association type polyurethane composite modified organic silicon softener intermediate;
(4) Secondary end capping: carrying out secondary end capping reaction on the multi-arm associative polyurethane composite modified organic silicon softener intermediate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether glycol, the rest of polymerization catalyst and the rest of diluent to prepare multi-arm associative polyurethane composite modified organic silicon softener macromolecules;
(4.1) putting the hydroxyl-terminated polyether glycol and hydroxyl-terminated alkyl polysiloxane in the step (2.2) and the rest of diluent into a reactor, and uniformly mixing;
(4.2) slowly adding the multi-arm association type polyurethane composite modified organosilicon softener intermediate in the step (3.4) within 38min at 83 ℃, and then carrying out heat preservation reaction for 37min;
(4.3) adding the residual catalyst, and continuing to react for 105min at 83 ℃ to prepare the multi-arm associated polyurethane composite modified organosilicon softener polymer;
(5) Mixing and emulsifying: mixing and emulsifying a multi-arm associative polyurethane composite modified organosilicon softener macromolecule, a neutralizer, an emulsifier, water and an organosilicon softener to prepare a multi-arm associative polyurethane composite modified organosilicon softener emulsion;
(5.1) cooling the material obtained in the step (4.3) to 40 ℃;
(5.2) adding an emulsifier, a neutralizer and a traditional commercial organosilicon softener, fully mixing, and keeping stirring and neutralizing for 25min;
(5.3) slowly and continuously adding water, stirring at a high speed, emulsifying uniformly, and keeping stirring for 25min;
and (5.4) standing and defoaming to prepare the multi-arm associated polyurethane composite modified organosilicon softener emulsion S2 (the solid content is 20.7%).
Example 3
(1) Preparing raw materials, wherein the specific selection and the dosage of the raw materials are shown in table 1;
(2) Dewatering pretreatment: respectively carrying out dehydration pretreatment on hydroxyl-terminated polyether triol and hydroxyl-terminated polyether diol under vacuum and heating conditions for later use;
(2.1) respectively putting hydroxyl-terminated polyether triol and hydroxyl-terminated polyether diol into different reactors;
(2.2) respectively treating at 108 deg.C and-0.100 MPa for 77 min;
(3) Primary end capping: carrying out primary end capping reaction on diisocyanate, hydroxyl-terminated polyether triol, partial polymerization catalyst and partial diluent to prepare a multi-arm associated polyurethane composite modified organosilicon softener intermediate;
(3.1) adding diisocyanate into a reactor, slowly adding 70% of hydroxyl-terminated polyether triol obtained in the step (2.2) within 47min at 78 ℃, and then carrying out heat preservation reaction for 27min;
(3.2) maintaining the reaction temperature at 78 ℃, adding the residual hydroxyl-terminated polyether triol obtained in the step (1.2) at one time, and then carrying out heat preservation reaction for 27min;
(3.3) adding 60% of diluent and 60% of polymerization catalyst into (3.2), and maintaining 83 ℃ for reaction for 27min;
(3.4) heating to 88 ℃, and reacting for 90min under the condition of heat preservation; cooling to 80 ℃, and then carrying out heat preservation reaction for 27min to obtain a multi-arm associated polyurethane composite modified organosilicon softener intermediate;
(4) Secondary end capping: carrying out secondary end capping reaction on the multi-arm associated polyurethane composite modified organic silicon softener intermediate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether glycol, the residual polymerization catalyst and the residual diluent to prepare a multi-arm associated polyurethane composite modified organic silicon softener macromolecule;
(4.1) putting the hydroxyl-terminated polyether glycol and hydroxyl-terminated alkyl polysiloxane in the step (3.2) and the rest of diluent into a reactor, and uniformly mixing;
(4.2) slowly adding the multi-arm associated polyurethane composite modified organosilicon softener intermediate in the step (34) within 37min at 82 ℃, and then carrying out heat preservation reaction for 38min;
(4.3) adding the residual catalyst, and continuing to react for 115min at 82 ℃ to prepare the multi-arm associated polyurethane composite modified organosilicon softener polymer;
(5) Mixing and emulsifying: mixing and emulsifying a multi-arm associative polyurethane composite modified organosilicon softener macromolecule, a neutralizer, an emulsifier, water and an organosilicon softener to prepare a multi-arm associative polyurethane composite modified organosilicon softener emulsion;
(5.1) cooling the material obtained in the step (4.3) to 40 ℃;
(5.2) adding an emulsifier, a neutralizer and a traditional commercial organosilicon softener, fully mixing, keeping stirring and neutralizing for 25min;
(5.3) slowly and continuously adding water, stirring at a high speed, emulsifying uniformly, and keeping stirring for 25min;
and (5.4) standing and defoaming to prepare the multi-arm associated polyurethane composite modified organosilicon softener emulsion S3 (the solid content is 21.4%).
Comparative example 1
Conventional amino-modified silicone softener D1 (ammonia number 0.6).
Test example
1. Cotton fabrics were finished using the softeners of examples and comparative examples using a drip diffusion method, and the hydrophilicity of the finished cotton fabrics was evaluated, with the results shown in table 2.
TABLE 2
| Comparative example 1 | Example 1 | Example 2 | Example 3 |
| 350 seconds | 35 seconds | 30 seconds | 25 seconds |
2. The cotton fabrics were finished using the softening agents of examples and comparative examples by the wrinkle recovery method, and the wrinkle recovery angle of the finished cotton fabrics was measured, and the results are shown in table 3.
TABLE 3
| Comparative example 1 | Example 1 | Example 2 | Example 3 |
| 10° | 60° | 65° | 85° |
The results of the test examples show that compared with the traditional amino modified organosilicon softener, the multi-arm associated polyurethane composite modified organosilicon softener emulsion prepared by the method can endow textiles with obviously better hydrophilicity and elastic hand feeling.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A preparation method of multi-arm association type polyurethane composite modified organosilicon softener emulsion is characterized by comprising the following steps:
(1) Preparing raw materials: the raw materials contain a polymerization monomer, an auxiliary agent, an organic silicon softening agent and water; wherein the polymeric monomer comprises diisocyanate, hydroxyl-terminated polyether triol, hydroxyl-terminated polysiloxane and hydroxyl-terminated polyether diol; the auxiliary agents comprise a polymerization catalyst, a diluent, a neutralizer and an emulsifier; the organosilicon softener is amino silicone oil; the water is soft water;
the diisocyanate is isophorone diisocyanate;
the hydroxyl-terminated polyether triol is a random copolymer of ethylene oxide and propylene oxide with the molecular weight of 2000-4000;
the hydroxyl-terminated polysiloxane is bishydroxyalkyl polymethylsilane with the molecular weight of 2000-4000;
the hydroxyl-terminated polyether glycol is polyethylene glycol with the molecular weight of 2000-3000;
the polymerization catalyst is stannous octoate or dibutyltin dilaurate;
the diluent is one or a mixture of two of acetone, butanone and ethyl pyrrolidone;
the neutralizer is acetic acid;
the emulsifier is one or a mixture of two of isomeric alcohol ether nonionic emulsifiers;
the polymerized monomer comprises the following components in parts by mole: 3.0 parts of diisocyanate, 1.0 part of hydroxyl-terminated polyether triol, 1.5-2.0 parts of hydroxyl-terminated polysiloxane and 1.0-1.5 parts of hydroxyl-terminated polyether glycol, wherein the sum of the mole parts of the hydroxyl-terminated polysiloxane and the hydroxyl-terminated polyether glycol is 2.7-3.1;
the dosage of the polymerization catalyst is 0.06-0.08 wt% of the total weight of the polymerization monomers;
the dosage of the diluent is 80 to 90 weight percent of the total weight of the polymerized monomers;
the dosage of the neutralizer is 0.3 to 0.6 weight percent of the weight of the amino silicone oil;
the dosage of the emulsifier is 6-12 wt% of the weight of the amino silicone oil;
the dosage of the amino silicone oil is 2 to 6 times of the total weight of the polymerized monomers;
the amount of water is adjusted to 20-30% of the solid content of the prepared multi-arm association type polyurethane composite modified organosilicon softener emulsion;
(2) Dewatering pretreatment: respectively carrying out dehydration pretreatment on hydroxyl-terminated polyether triol and hydroxyl-terminated polyether glycol under vacuum and heating conditions for later use;
(3) Primary end capping: carrying out primary end capping reaction on diisocyanate, hydroxyl-terminated polyether triol, a part of polymerization catalyst and a part of diluent to prepare a multi-arm associated polyurethane composite modified organosilicon softener intermediate;
(4) Secondary end capping: carrying out secondary end capping reaction on the multi-arm associated polyurethane composite modified organic silicon softener intermediate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether glycol, the residual polymerization catalyst and the residual diluent to prepare a multi-arm associated polyurethane composite modified organic silicon softener macromolecule;
(5) Mixing and emulsifying: mixing and emulsifying the multi-arm associative polyurethane composite modified organic silicon softener macromolecule, the neutralizer, the emulsifier, the water and the organic silicon softener to prepare the multi-arm associative polyurethane composite modified organic silicon softener emulsion.
2. The preparation method of the multi-arm associative polyurethane composite modified silicone softener emulsion according to claim 1, wherein the step (2) is specifically as follows:
(2.1) respectively putting hydroxyl-terminated polyether triol and hydroxyl-terminated polyether diol into different reactors;
(2.2) treating at 105-110 ℃ and-0.100-0.098 MPa vacuum degree for 70-80 min for later use.
3. The preparation method of the multi-arm associated polyurethane composite modified silicone softener emulsion according to claim 1 or 2, wherein the step (3) is specifically:
(3.1) adding diisocyanate into a reactor, adding 50-70% of the hydroxyl-terminated polyether triol obtained in the step (2) within 40-60 min at 70-80 ℃, and then carrying out heat preservation reaction for 20-30 min;
(3.2) maintaining the reaction temperature at 70-80 ℃, adding the rest of the hydroxyl-terminated polyether triol obtained in the step (2), and then carrying out heat preservation reaction for 20-30 min;
(3.3) adding 40-60% of diluent and 40-60% of polymerization catalyst into (3.2), and reacting for 20-30 min at 75-85 ℃;
(3.4) heating to 86-90 ℃, and reacting for 60-90 min under the condition of heat preservation; cooling to 77-83 ℃, and then carrying out heat preservation reaction for 20-30 min to obtain the multi-arm association type polyurethane composite modified organosilicon softener intermediate.
4. The preparation method of the multi-arm associative polyurethane composite modified silicone softener emulsion according to claim 1 or 2, wherein the step (4) is specifically:
(4.1) putting the hydroxyl-terminated polyether glycol obtained in the step (2), hydroxyl-terminated polysiloxane and the rest of diluent into a reactor, and uniformly mixing;
(4.2) adding the multi-arm associated polyurethane composite modified organosilicon softener intermediate obtained in the step (3) within 30-40 min at 80-85 ℃, and then carrying out heat preservation reaction for 30-40 min;
(4.3) adding the residual catalyst, and continuing to react for 90-120 min at the temperature of 80-85 ℃ to prepare the multi-arm associated polyurethane composite modified organosilicon softener polymer.
5. The preparation method of the multi-arm associative polyurethane composite modified silicone softener emulsion according to claim 1 or 2, wherein the step (5) is specifically:
(5.1) cooling the material obtained in the step (4) to 35-45 ℃;
(5.2) adding an emulsifier, a neutralizer and an organic silicon softening agent, fully mixing and maintaining stirring for neutralization for 20-30 min;
(5.3) adding water, stirring at a high speed, emulsifying uniformly, and keeping stirring for 20-30 min;
and (5.4) standing and defoaming to prepare the multi-arm associated polyurethane composite modified organosilicon softener emulsion.
6. The preparation method of the multi-arm associative polyurethane composite modified silicone softener emulsion according to claim 1, wherein the amino silicone oil is an amino silicone oil with an ammonia value of 0.3-0.6 and a solid content of 60-80%.
7. The preparation method of the multi-arm associative polyurethane composite modified silicone softener emulsion according to claim 1, wherein the water is soft water with total hardness of less than 5 degrees.
8. The preparation method of the multi-arm associative polyurethane composite modified silicone softener emulsion according to claim 1, wherein the amount of the diluent is 80.5-88 wt% of the total weight of the polymerized monomers.
9. The preparation method of the multi-arm associated polyurethane composite modified silicone softener emulsion according to claim 1, wherein the amount of the emulsifier is 8-10 wt% of the weight of the amino silicone oil.
10. The multi-arm associative polyurethane composite modified silicone softener emulsion prepared by the method of any one of claims 1 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103497307A (en) * | 2013-10-22 | 2014-01-08 | 武汉纺织大学 | Preparation method of quaternary ammonium type positive ion polyurethane base polyether block hydrophilic silicone softener ultra-micro emulsion and product thereof |
| CN103497308A (en) * | 2013-10-22 | 2014-01-08 | 武汉纺织大学 | Low temperature high elastic type waterproof antifouling water-based polyurethane finishing agent preparing method and product |
| CN104774307A (en) * | 2015-04-08 | 2015-07-15 | 武汉纺织大学 | Preparation method and product of modified polyurethane flexible high-molecular emulsion containing side long chain alkyl |
| CN109970945A (en) * | 2019-04-10 | 2019-07-05 | 武汉纺织大学 | A kind of organic-silicon-modified weak amphoteric ion type polyaminoester emulsion and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497307A (en) * | 2013-10-22 | 2014-01-08 | 武汉纺织大学 | Preparation method of quaternary ammonium type positive ion polyurethane base polyether block hydrophilic silicone softener ultra-micro emulsion and product thereof |
| CN103497308A (en) * | 2013-10-22 | 2014-01-08 | 武汉纺织大学 | Low temperature high elastic type waterproof antifouling water-based polyurethane finishing agent preparing method and product |
| CN104774307A (en) * | 2015-04-08 | 2015-07-15 | 武汉纺织大学 | Preparation method and product of modified polyurethane flexible high-molecular emulsion containing side long chain alkyl |
| CN109970945A (en) * | 2019-04-10 | 2019-07-05 | 武汉纺织大学 | A kind of organic-silicon-modified weak amphoteric ion type polyaminoester emulsion and preparation method thereof |
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