CN112981963B - Net-shaped association type polyurethane composite modified organic silicon softener emulsion and preparation method thereof - Google Patents
Net-shaped association type polyurethane composite modified organic silicon softener emulsion and preparation method thereof Download PDFInfo
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- CN112981963B CN112981963B CN202110182821.1A CN202110182821A CN112981963B CN 112981963 B CN112981963 B CN 112981963B CN 202110182821 A CN202110182821 A CN 202110182821A CN 112981963 B CN112981963 B CN 112981963B
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention relates to the field of polyurethane modified organosilicon softener emulsion for finishing the hand feeling and style of various textiles, and discloses a reticular association type polyurethane composite modified organosilicon softener emulsion and a preparation method thereof. The method comprises the following steps: preparing raw materials; dewatering pretreatment; pre-polymerization; chain extension; mixing and emulsifying. The softening agent emulsion has a novel structure and an obvious effect. Various macromolecules in the composite emulsion can be effectively associated with each other, and the blending modification of the traditional organosilicon softening agent on textile fibers is realized in an intermolecular entanglement mode. The self-made polyurethane modified polysiloxane macromolecules have long-chain cross-linking chains with low cross-linking degree, and polysiloxane long chains and polyether long chains are distributed in a gradient manner in the lateral direction of the cross-linking chains. Compared with the traditional organic silicon softening agent, the product of the invention can endow various textiles with obviously better hydrophilicity and 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) organic silicon softener emulsion for finishing hand feeling styles of various textiles, in particular to reticular association type polyurethane composite modified organic silicon softener emulsion and a preparation method thereof.
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 the structure of the aqueous polyurethane, the relevant research and development work has focused essentially on the complex modification of silicone emulsions with polyurethanes. However, the water-based polyurethane lacks a common structure with the silicone softener and has a great polarity difference, so that the water-based polyurethane and the silicone softener have incompatibility and poor compatibility in terms of chemical structure, 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 raw materials of the reactive organosilicon modified cationic waterborne polyurethane comprise a polymerized monomer, a modified monomer, an auxiliary agent and water, wherein: the polymerization monomer comprises diisocyanate, an ionic chain extender and a nonionic chain extender; the modified monomer is polysiloxane, silane coupling agent and poly-butadiene; the auxiliary agent comprises a neutralizing agent and a diluting agent.
For example, a preparation method of reactive organosilicon modified cationic waterborne polyurethane disclosed by ' cationic waterborne polyurethane FS20566M ' (No. 5 of 24 of 2009 polyurethane industry) ' by Yanbungan, Yangjo, Tangli and the like comprises the following raw materials: the polymerization monomer is isophorone diisocyanate, ionic chain extender N-methyldiethanolamine and non-ionic chain extender trimethylolpropane; the modified monomer is hydroxyalkyl modified polysiloxane, aminopropyl trimethoxy silane coupling agent and poly-cis-butadiene; the auxiliary agent is neutralizing agent acetic acid and diluting agent N-methyl pyrrolidone; the emulsifying medium is deionized water.
In the method, the completely non-hydrophilic poly-butadiene is used as a soft polyurethane monomer and the non-ionic trifunctional micromolecule monomer trimethylolpropane is used as a chain extender, so that the product is not easy to emulsify, and the emulsion has larger particle size, wider particle size distribution and low stability; meanwhile, due to the lack of a common structure (polysiloxane chain segment) with the organosilicon softener and the introduction of higher-density cross-linking by the trimethylolpropane and aminopropyltrimethoxysilane coupling agents, the organosilicon softener cannot be effectively entangled with molecules of the trimethylolpropane and aminopropyltrimethoxysilane coupling agents, and is not suitable for the composite modification of the traditional organosilicon softener.
2. The raw materials of the hydrophilic composite modified organosilicon softener comprise a nonionic surfactant, a terpolymer silicone oil softener and an amino silicone oil softener, wherein the terpolymer silicone oil softener is polyether block amino polysiloxane softener emulsion with the solid content of 77 percent; the amino silicone oil softener is a series of traditional amino polysiloxane softener emulsions with different viscosities (molecular weights).
The preparation method of the hydrophilic composite modified organosilicon softener disclosed by the ternary polymerization organosilicon softener complex soft finishing of cotton fabrics of Linjing, Zhongxiang and Sunzhongliang (the 13 th period in 2015 from printing and dyeing) has the specific technical scheme that: a nonionic surfactant Lutensol XP50 (basf) is used as an emulsifier, 30 mass percent (relative to non-volatile components of ternary copolymer silicone oil) is prepared into ternary copolymer silicone oil microemulsion, and the ternary copolymer silicone oil microemulsion is compounded with amino silicone oil emulsion Rodorsil 21650 to prepare the hydrophilic composite modified organic silicon softener emulsion.
According to the method, on the basis of researching the self-emulsifying property and the softening effect of the terpolymer silicone oil, the terpolymer silicone oil is compounded with different softening agents to carry out softening finishing on cotton fabrics, so that the finished products are endowed with soft and smooth handfeel, and meanwhile, the hydrophilicity of the finished products is not obviously reduced. The obtained emulsion treated cotton fabric has good wettability, and the softness, smoothness, hydrophilicity and whiteness of the fabric are all improved compared with the single use of the self-emulsifying ternary copolymerized silicone oil. However, the method mainly uses a special emulsifier to improve the hydrophilicity of the organic silicon softener, and does not introduce a non-silicon long-chain structure with special style effect into a polysiloxane softener polymer by a chemical means. Therefore, the hand feeling style of the product still can not be separated from the range of the organic silicon softening agent, and a novel hand feeling style can not be obtained. Certainly, the novel and changeable hand feeling style characteristics cannot be brought by blending and modifying the organic silicon softening agent with the traditional organic silicon softening agent.
3. 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 organosilicon 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 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 reticular association type polyurethane composite modified organic silicon 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 elastic soft style of various textiles. Various macromolecules in the reticular 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 macromolecules have long-chain cross-linking chains with low cross-linking degree, and polysiloxane long chains and polyether long chains are distributed in a gradient manner in the lateral direction of the cross-linking chains. Compared with the traditional organic silicon softening agent, the product of the invention can endow various textiles with obviously better hydrophilicity and 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, the present invention provides a method for preparing a reticular association type 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 polymerization monomer comprises diisocyanate, hydroxyl-terminated polyether triol, hydroxyl-terminated polysiloxane, a functional chain extender and a cationic chain extender; 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 3000-4000;
the hydroxyl-terminated polysiloxane is a mixture of single-ended dihydroxyalkyl polymethylsilane with the molecular weight of 6000-9000 and double-ended dihydroxyalkyl polymethylsilane with the molecular weight of 2000-3000;
the functional chain extender is single-ended dihydroxy hydrocarbon polyglycol ether with the molecular weight of 1000-1500;
the cationic chain extender is N-methyldiethanolamine or N-butyldiethanolamine;
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: 1.00 parts of diisocyanate, 0.01-0.02 part of hydroxyl-terminated polyether triol, 0.25-0.35 part of hydroxyl-terminated polysiloxane, 0.25-0.35 part of functional chain extension and 0.50-0.60 part of cationic chain extender, wherein the sum of the mole parts of the hydroxyl-terminated polyether triol, the hydroxyl-terminated polysiloxane, the functional chain extension and the cationic chain extender is 1.10-1.30 parts; wherein the molar ratio of the single-end dihydroxyalkyl polymethylsilane to the double-end dihydroxyalkyl polymethylsilane is 1 (10-15);
the dosage of the polymerization catalyst is 0.04-0.06 wt% of the total weight of the polymerization monomers;
the dosage of the diluent is 70-80 wt% of the total weight of the polymerized monomers;
the dosage of the neutralizer is 2-2.5 times of the weight of the cationic chain extender;
the using amount of the emulsifier is 7-15% of the weight of the amino silicone oil;
the dosage of the amino silicone oil is 3-9 times of the total weight of the polymerized monomers;
the amount of water is adjusted to ensure that the solid content of the prepared reticular associating type polyurethane composite modified organosilicon softener emulsion is 20-30%;
(2) dewatering pretreatment: respectively carrying out dehydration pretreatment on the functional chain extender and the hydroxyl-terminated polyether triol under the vacuum and heating conditions for later use;
(3) pre-polymerization: carrying out prepolymerization reaction on diisocyanate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether triol and a polymerization catalyst to prepare a reticular associated polyurethane composite modified organosilicon softener prepolymer;
(4) chain extension: carrying out chain extension reaction on the reticular association type polyurethane composite modified organic silicon softener prepolymer, a functional chain extender, a cation chain extender and a diluent to prepare reticular association type polyurethane composite modified organic silicon softener macromolecules;
(5) mixing and emulsifying: mixing and emulsifying the reticular associative polyurethane composite modified organic silicon softener polymer, a neutralizer, an emulsifier, water and an organic silicon softener to prepare the reticular associative polyurethane composite modified organic silicon softener emulsion.
Preferably, the step (2) is specifically:
(2.1) respectively putting the functional chain extender and the hydroxyl-terminated polyether triol into different reactors;
(2.2) respectively treating at 105-110 ℃ and-0.100-0.098 MPa vacuum degree for 70-80 min for later use.
Preferably, the step (3) is specifically:
(3.1) adding diisocyanate into a reactor, adding hydroxyl-terminated polysiloxane and hydroxyl-terminated polyether triol subjected to dehydration pretreatment in the step (2) into the reactor at 70-80 ℃ within 10-20 min, and carrying out heat preservation reaction for 20-30 min;
(3.2) adding a polymerization catalyst into the mixture obtained in the step (3.1), and reacting for 15-20 min while maintaining the temperature at 75-85 ℃;
(3.3) heating to 88-92 ℃, and reacting for 80-100 min in a heat preservation manner; and cooling to 77-83 ℃, and then carrying out heat preservation reaction for 20-40 min to obtain the prepolymer of the reticular association type polyurethane composite modified organosilicon softener.
Preferably, the step (4) is specifically:
(4.1) uniformly mixing the functional chain extender subjected to dehydration pretreatment in the step (2) with a cationic chain extender and a diluent of 1/2 for later use;
(4.2) adding 20% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organic silicon softening agent prepared in the step (3), and reacting for 50-70 min at 77-83 ℃;
(4.3) continuously adding 40% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3), reacting for 50-70 min at the temperature of 80-84 ℃, and adding 1/2 diluent to adjust the viscosity of a reaction system;
(4.4) continuously adding 40% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organic silicon softening agent prepared in the step (3), and reacting for 50-70 min at the temperature of 80-84 ℃;
and (4.5) heating to 86-90 ℃, and reacting for 50-70 min to obtain the reticular association type 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 ℃, adding a neutralizing agent, stirring and neutralizing for 20-30 min;
(5.2) adding an emulsifier and an organic silicon softening agent, fully mixing, and keeping stirring and neutralizing for 20-30 min;
(5.3) adding water, stirring at a high speed, emulsifying uniformly, and keeping stirring for 15-20 min;
and (5.4) standing and defoaming to prepare the reticular association type 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 72 to 78 wt% based on the total weight of the polymerized monomers.
Preferably, the amount of the emulsifier is 9-14% of the weight of the amino silicone oil.
The invention provides a reticular associating type polyurethane composite modified organic silicon 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 manner. Namely: according to the idea of 'innovation of chemical and physical structures', an organic silicon chain link, a polyether chain link and a cationic/nonionic aqueous polyurethane chain link are combined with each other in a specially designed position relationship, and technical measures such as 'chemical block, graft modification, gradual polymerization, long-chain crosslinking and stepwise chain extension' are adopted to realize special distribution of special chain links on a polymer skeleton and obtain a novel style effect.
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 links, groups, structure distribution and the like) and supermolecular structure (micro-crosslinking) design of organosilicon/polyurethane/polyether nonlinear hybrid macromolecules are realized. The self-made polyurethane modified polysiloxane polymer has a special 'macroporous long-chain micro-crosslinking' structure, can form a stable 'forced mutual solubility' structure with the traditional organic silicon softener polymer, and provides guarantee for the application performance (elasticity, hydrophilicity and the like) of the product. In fact, according to the formula and the design of the polymerization process, the product should be a mixture of comb-shaped and mesh-shaped macromolecules, and the complex product composition further leads to a more complex and stable intermolecular entanglement structure with the traditional organosilicon softener macromolecule, thereby being beneficial to obtaining a remarkable modification effect.
3. In the invention, based on the chemical and special supermolecular structural design of polyurethane and polysiloxane nonlinear multi-hybrid macromolecules, the distribution of special structures on a product macromolecule framework and a stage structural design and control method are researched, and the complicated nonlinear (net-shaped + comb-shaped) multi-hybrid organic silicon modified polyurethane macromolecules are realized through reaction conditions and control thereof, monomer proportioning design, feeding sequence design, feeding speed design and the like.
4. In the invention, the obtained product and various polysiloxane (organosilicon) softening agents can form a sufficient intermolecular entangled structure, the two have good compatibility and compatibility, and a polyurethane structure and a functional structure (polyether, cation, cross-linking and the like) can be effectively introduced into a softening agent 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 hydrophilic and elastic handfeel.
5. In the invention, the reticular polyether type organic silicon modified polyurethane (similar to a polyurethane surfactant) is used as the emulsifier of the amino silicone oil, so that the aim of compound modification of the amino silicone oil is fulfilled, the use of the emulsifier is greatly reduced, and the preparation method is safe, environment-friendly, convenient to use and good in 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, and the mutual separation of the product and the traditional organic silicon softener macromolecule in a heat treatment process is effectively inhibited; meanwhile, the product has the application performance characteristics brought by various chemical structures such as polysiloxane, polyurethane, polyether, polar groups and the like, and the product has better compatibility with the organic silicon softener, so that the compound has rich hand feeling, obvious characteristics and convenient use.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present 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 ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a reticular association type 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 polymerization monomer comprises diisocyanate, hydroxyl-terminated polyether triol, hydroxyl-terminated polysiloxane, a functional chain extender and a cationic chain extender; 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 3000-4000;
the hydroxyl-terminated polysiloxane is a mixture of single-ended dihydroxyalkyl polymethylsilane with the molecular weight of 6000-9000 and double-ended dihydroxyalkyl polymethylsilane with the molecular weight of 2000-3000;
the functional chain extender is single-ended dihydroxy hydrocarbon polyglycol ether with the molecular weight of 1000-1500;
the cationic chain extender is N-methyldiethanolamine or N-butyldiethanolamine;
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: 1.00 of diisocyanate, 0.01-0.02 of hydroxyl-terminated polyether triol, 0.25-0.35 of hydroxyl-terminated polysiloxane, 0.25-0.35 of functional chain extension and 0.50-0.60 of cationic chain extender, wherein the sum of the mole parts of the hydroxyl-terminated polyether triol, the hydroxyl-terminated polysiloxane, the functional chain extension and the cationic chain extender is 1.10-1.30; wherein the molar ratio of the single-end dihydroxyalkyl polymethylsilane to the double-end dihydroxyalkyl polymethylsilane is 1 (10-15);
the dosage of the polymerization catalyst is 0.04-0.06 wt% of the total weight of the polymerization monomers;
the dosage of the diluent is 70-80 wt% of the total weight of the polymerized monomers;
the dosage of the neutralizer is 2-2.5 times of the weight of the cationic chain extender;
the using amount of the emulsifier is 7-15% of the weight of the amino silicone oil;
the dosage of the amino silicone oil is 3-9 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 reticular association type polyurethane composite modified organosilicon softener emulsion;
(2) dewatering pretreatment: respectively dehydrating and pretreating the functional chain extender and the hydroxyl-terminated polyether triol under vacuum and heating conditions for later use;
(3) pre-polymerization: carrying out prepolymerization reaction on diisocyanate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether triol and a polymerization catalyst to prepare a reticular association type polyurethane composite modified silicone softener prepolymer;
(4) chain extension: carrying out chain extension reaction on the reticular association type polyurethane composite modified organic silicon softener prepolymer, a functional chain extender, a cation chain extender and a diluent to prepare reticular association type polyurethane composite modified organic silicon softener macromolecules;
(5) mixing and emulsifying: mixing and emulsifying the reticular association type polyurethane composite modified organic silicon softener macromolecule, the neutralizer, the emulsifier, the water and the organic silicon softener to prepare the reticular association type polyurethane composite modified organic silicon softener emulsion.
In particular embodiments, the polymerization catalyst may be used in an amount of 0.04 wt%, 0.042 wt%, 0.044 wt%, 0.046 wt%, 0.048 wt%, 0.05 wt%, 0.052 wt%, 0.054 wt%, 0.056 wt%, 0.058 wt%, or 0.06 wt% based on the total weight of the polymerized monomers.
In particular embodiments, the neutralizing agent may be used in an amount of 2 times, 2.1 times, 2.2 times, 2.3 times, 2.4 times, or 2.5 times the weight of the cationic chain extender.
In particular embodiments, the amino silicone oil may be used in an amount of 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, or 9 times the total weight of the polymerized monomers.
In the invention, the solid content of the obtained reticular associating type polyurethane composite modified organosilicon softener emulsion is controlled by controlling the using amount of water. In specific embodiments, the solid content of the reticular associating type polyurethane composite modified silicone softener emulsion can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%.
In a preferred embodiment, the step (2) is specifically:
(2.1) respectively putting the functional chain extender and the hydroxyl-terminated polyether triol into different reactors;
(2.2) respectively 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 hydroxyl-terminated polysiloxane and hydroxyl-terminated polyether triol subjected to dehydration pretreatment in the step (2) into the reactor at 70-80 ℃ within 10-20 min, and carrying out heat preservation reaction for 20-30 min;
(3.2) adding a polymerization catalyst into the mixture obtained in the step (3.1), and reacting for 15-20 min while maintaining the temperature at 75-85 ℃;
(3.3) heating to 88-92 ℃, and reacting for 80-100 min in a heat preservation manner; and (3) cooling to 77-83 ℃, and then carrying out heat preservation reaction for 20-40 min to obtain the reticular association type polyurethane composite modified organosilicon softener prepolymer.
In the invention, in the step (3.1), the hydroxyl-terminated polysiloxane is added within 10-20 min, which is a slow addition process.
In a preferred embodiment, the step (4) is specifically:
(4.1) uniformly mixing the functional chain extender subjected to dehydration pretreatment in the step (2) with a cationic chain extender and a diluent of 1/2 for later use;
(4.2) adding 20% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organic silicon softening agent prepared in the step (3), and reacting for 50-70 min at 77-83 ℃;
(4.3) continuously adding 40% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3), reacting for 50-70 min at the temperature of 80-84 ℃, and adding 1/2 diluent to adjust the viscosity of a reaction system;
(4.4) continuously adding 40% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3), and reacting for 50-70 min at the temperature of 80-84 ℃;
and (4.5) heating to 86-90 ℃, and reacting for 50-70 min to obtain the reticular association type polyurethane composite modified organosilicon softener polymer.
In the present invention, in step (4.3), there is no particular requirement for the timing of addition of the diluent, and it may be added as needed.
In a preferred embodiment, the step (5) is specifically:
(5.1) cooling the material obtained in the step (4) to 35-45 ℃, adding a neutralizing agent, stirring and neutralizing for 20-30 min;
(5.2) adding an emulsifier and an organic silicon softening agent, fully mixing, and keeping stirring and neutralizing for 20-30 min;
(5.3) adding water, stirring at a high speed, emulsifying uniformly, and keeping stirring for 15-20 min;
and (5.4) standing and defoaming to prepare the reticular association type 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 72 to 78 wt% based on the total weight of the polymerized monomers.
In particular embodiments, the diluent may be used in an amount of 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, or 80 wt% of the total weight of the polymerized monomers.
In a preferred embodiment, the emulsifier is used in an amount of 9 to 14% by weight of the amino silicone oil.
In particular embodiments, the emulsifier may be used in an amount of 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15% by weight of the aminosilicone.
The invention provides a reticular associating type polyurethane composite modified organic silicon 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. The product prepared by the invention can endow various textiles with obviously better hydrophilicity and elastic hand feeling, and compared with the traditional amino modified organosilicon softener, the product has the following advantages: the hydrophilicity of the finished cotton fabric can be shortened from 300-400 s to 15-30 s, and the wrinkle recovery angle can be increased from about 10 degrees to 40-60 degrees. The finished product should be stored in a shady, cool and dry place in a sealed manner.
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 dehydrating and pretreating the functional chain extender and the hydroxyl-terminated polyether triol under vacuum and heating conditions for later use;
(2.1) respectively putting the functional chain extender and the hydroxyl-terminated polyether triol into different reactors;
(2.2) respectively treating at 107 deg.C and-0.099 MPa for 77 min;
(3) pre-polymerization: carrying out prepolymerization reaction on diisocyanate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether triol and a polymerization catalyst to prepare a reticular association type polyurethane composite modified silicone softener prepolymer;
(3.1) adding diisocyanate into a reactor, slowly adding hydroxyl-terminated polysiloxane and the hydroxyl-terminated polyether triol obtained in the step (3.2) at 72 ℃ within 17min, and reacting for 22min under heat preservation;
(3.2) adding a polymerization catalyst into the mixture (3.1) and maintaining the temperature at 80 ℃ for reacting for 17 min;
(3.3) heating to 90 ℃, and keeping the temperature to react for 87 min; cooling to 80 ℃, and then carrying out heat preservation reaction for 32min to obtain a prepolymer of the reticular association type polyurethane composite modified organosilicon softener;
(4) chain extension: carrying out chain extension reaction on the reticular association type polyurethane composite modified organic silicon softener prepolymer, a functional chain extender, a cation chain extender and a diluent to prepare reticular association type polyurethane composite modified organic silicon softener macromolecules;
(4.1) uniformly mixing the functional chain extender obtained in the step (2.2), the cationic chain extender and the diluent of 1/2 for later use;
(4.2) adding 20% of the mixture in the step (3.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3.3), and reacting for 57min at 80 ℃;
(4.3) continuously adding 40% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3.3), reacting for 57min at 82 ℃, and timely adding 1/2 diluent to adjust the viscosity of a reaction system;
(4.4) continuously adding 40% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3.3), and reacting for 57min at 82 ℃;
(4.5) heating to 88 ℃, and reacting for 60min to prepare the reticular association type polyurethane composite modified organosilicon softener polymer;
(5) mixing and emulsifying: mixing and emulsifying a reticular association type polyurethane composite modified organic silicon softener macromolecule, a neutralizer, an emulsifier, water and an organic silicon softener to prepare a reticular association type polyurethane composite modified organic silicon softener emulsion;
(5.1) cooling the material obtained in the step (4.5) to 40 ℃, adding a neutralizing agent, stirring and neutralizing for 25 min;
(5.2) adding an emulsifier and a traditional commercial organosilicon softener, fully mixing, and keeping stirring and neutralizing for 25 min;
(5.3) slowly and continuously adding water, stirring at a high speed, emulsifying uniformly, and keeping stirring for 20 min;
and (5.4) standing and defoaming to prepare the reticular association type polyurethane composite modified organosilicon softener emulsion S1 (the solid content is 23.6%).
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 dehydrating and pretreating the functional chain extender and the hydroxyl-terminated polyether triol under vacuum and heating conditions for later use;
(2.1) respectively putting the functional chain extender and the hydroxyl-terminated polyether triol into different reactors;
(2.2) respectively treating at 107 deg.C and-0.099 MPa for 78 min;
(3) pre-polymerization: carrying out prepolymerization reaction on diisocyanate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether triol and a polymerization catalyst to prepare a reticular associated polyurethane composite modified organosilicon softener prepolymer;
(3.1) adding diisocyanate into a reactor, slowly adding hydroxyl-terminated polysiloxane and the hydroxyl-terminated polyether triol obtained in the step (2.2) at 75 ℃ within 15min, and reacting for 25min under the condition of heat preservation;
(3.2) adding a polymerization catalyst into the mixture obtained in the step (3.1) and maintaining the temperature at 80 ℃ for reacting for 18 min;
(3.3) heating to 90 ℃, and reacting for 90min under the condition of heat preservation; cooling to 80 ℃, and then carrying out heat preservation reaction for 38min to obtain a prepolymer of the reticular association type polyurethane composite modified organosilicon softener;
(4) chain extension: carrying out chain extension reaction on the reticular association type polyurethane composite modified organic silicon softener prepolymer, the functional chain extender, the cationic chain extender and the diluent to prepare a reticular association type polyurethane composite modified organic silicon softener macromolecule;
(4.1) uniformly mixing the functional chain extender obtained in the step (2.2), the cationic chain extender and the diluent 1/2 for later use;
(4.2) adding 20% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3.3), and reacting for 68min at 80 ℃;
(4.3) continuously adding 40% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3.3), reacting for 68min at 82 ℃, and timely adding 1/2 diluent to adjust the viscosity of a reaction system;
(4.4) continuously adding 40% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3.3), and reacting for 68min at 82 ℃;
(4.5) heating to 88 ℃, and reacting for 60min to prepare the reticular association type polyurethane composite modified organosilicon softener polymer;
(5) mixing and emulsifying: mixing and emulsifying a reticular association type polyurethane composite modified organic silicon softener macromolecule, a neutralizer, an emulsifier, water and an organic silicon softener to prepare a reticular association type polyurethane composite modified organic silicon softener emulsion;
(5.1) cooling the material obtained in the step (4.5) to 40 ℃, adding a neutralizing agent, stirring and neutralizing for 25 min;
(5.2) adding an emulsifier and a traditional commercial organosilicon softener, fully mixing, and keeping stirring and neutralizing for 25 min;
(5.3) slowly and continuously adding water, stirring at a high speed, emulsifying uniformly, and keeping stirring for 20 min;
and (5.4) standing and defoaming to prepare the reticular association type polyurethane composite modified organosilicon softener emulsion S2 (the solid content is 23.7%).
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 dehydrating and pretreating the functional chain extender and the hydroxyl-terminated polyether triol under vacuum and heating conditions for later use;
(2.1) respectively putting the functional chain extender and the hydroxyl-terminated polyether triol into different reactors;
(2.2) treating at 107 deg.C and-0.099 MPa for 77 min.
(3) Prepolymerization: carrying out prepolymerization reaction on diisocyanate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether triol and a polymerization catalyst to prepare a reticular associated polyurethane composite modified organosilicon softener prepolymer;
(3.1) adding diisocyanate into a reactor, slowly adding hydroxyl-terminated polysiloxane and the hydroxyl-terminated polyether triol obtained in the step (2.2) at 78 ℃ within 13min, and reacting for 27min under heat preservation;
(3.2) adding a polymerization catalyst into the mixture obtained in the step (3.1) and maintaining the temperature at 82 ℃ for reacting for 17 min;
(3.3) heating to 90 ℃, and keeping the temperature for reaction for 97 min; cooling to 80 ℃, and then carrying out heat preservation reaction for 38min to obtain a prepolymer of the reticular association type polyurethane composite modified organosilicon softener;
(4) chain extension: carrying out chain extension reaction on the reticular association type polyurethane composite modified organic silicon softener prepolymer, the functional chain extender, the cationic chain extender and the diluent to prepare a reticular association type polyurethane composite modified organic silicon softener macromolecule;
(4.1) uniformly mixing the functional chain extender obtained in the step (2.2), the cationic chain extender and the diluent of 1/2 for later use;
(4.2) adding 20% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3.3), and reacting for 37min at 80 ℃;
(4.3) adding 40% of the mixture in (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in (3.3), reacting for 67min at 82 ℃, and adding 1/2 diluent to adjust the viscosity of a reaction system at proper time;
(4.4) adding 40% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3.3), and reacting for 67min at 82 ℃;
(4.5) heating to 88 ℃, and reacting for 68min to prepare the reticular associated polyurethane composite modified organosilicon softener polymer;
(5) mixing and emulsifying: mixing and emulsifying a reticular association type polyurethane composite modified organic silicon softener macromolecule, a neutralizer, an emulsifier, water and an organic silicon softener to prepare a reticular association type polyurethane composite modified organic silicon softener emulsion;
(5.1) cooling the material obtained in the step (4.5) to 40 ℃, adding a neutralizing agent, stirring and neutralizing for 25 min;
(5.2) adding an emulsifier and a traditional commercial organosilicon softener, fully mixing, and keeping stirring and neutralizing for 25 min;
(5.3) slowly and continuously adding water, stirring at a high speed, emulsifying uniformly, and keeping stirring for 20 min;
and (5.4) standing and defoaming to prepare the reticular association type polyurethane composite modified organosilicon softener emulsion S3 (the solid content is 23.6%).
Comparative example 1
Conventional amino-modified silicone softener D1 (ammonia number 0.6).
Test example
1. The 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 examined, and the results are shown in table 2.
TABLE 2
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° | 45° | 55° | 50° |
The results of the test examples show that compared with the traditional amino modified organosilicon softener, the reticular associative 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 a reticular 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 polymerization monomer comprises diisocyanate, hydroxyl-terminated polyether triol, hydroxyl-terminated polysiloxane, a functional chain extender and a cationic chain extender; 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 3000-4000;
the hydroxyl-terminated polysiloxane is a mixture of single-ended dihydroxyalkyl polymethylsilane with the molecular weight of 6000-9000 and double-ended dihydroxyalkyl polymethylsilane with the molecular weight of 2000-3000;
the functional chain extender is single-ended dihydroxy hydrocarbon polyglycol ether with the molecular weight of 1000-1500;
the cationic chain extender is N-methyldiethanolamine or N-butyldiethanolamine;
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: 1.00 of diisocyanate, 0.01-0.02 of hydroxyl-terminated polyether triol, 0.25-0.35 of hydroxyl-terminated polysiloxane, 0.25-0.35 of functional chain extension and 0.50-0.60 of cationic chain extender, wherein the sum of the mole parts of the hydroxyl-terminated polyether triol, the hydroxyl-terminated polysiloxane, the functional chain extension and the cationic chain extender is 1.10-1.30; wherein the molar ratio of the single-end dihydroxyalkyl polymethylsilane to the double-end dihydroxyalkyl polymethylsilane is 1 (10-15);
the dosage of the polymerization catalyst is 0.04-0.06 wt% of the total weight of the polymerization monomers;
the dosage of the diluent is 70-80 wt% of the total weight of the polymerized monomers;
the dosage of the neutralizer is 2-2.5 times of the weight of the cationic chain extender;
the using amount of the emulsifier is 7-15% of the weight of the amino silicone oil;
the dosage of the amino silicone oil is 3-9 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 reticular association type polyurethane composite modified organosilicon softener emulsion;
(2) dewatering pretreatment: respectively dehydrating and pretreating the functional chain extender and the hydroxyl-terminated polyether triol under vacuum and heating conditions for later use;
(3) pre-polymerization: carrying out prepolymerization reaction on diisocyanate, hydroxyl-terminated polysiloxane, hydroxyl-terminated polyether triol and a polymerization catalyst to prepare a reticular associated polyurethane composite modified organosilicon softener prepolymer;
(4) chain extension: carrying out chain extension reaction on the reticular association type polyurethane composite modified organic silicon softener prepolymer, a functional chain extender, a cation chain extender and a diluent to prepare reticular association type polyurethane composite modified organic silicon softener macromolecules;
(5) mixing and emulsifying: mixing and emulsifying the reticular associative polyurethane composite modified organic silicon softener polymer, a neutralizer, an emulsifier, water and an organic silicon softener to prepare the reticular associative polyurethane composite modified organic silicon softener emulsion.
2. The preparation method of the reticular associative polyurethane composite modified silicone softener emulsion according to claim 1, wherein the step (2) is specifically:
(2.1) respectively putting the functional chain extender and the hydroxyl-terminated polyether triol into different reactors;
(2.2) respectively 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 reticular associative 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 hydroxyl-terminated polysiloxane and hydroxyl-terminated polyether triol subjected to dehydration pretreatment in the step (2) into the reactor at 70-80 ℃ within 10-20 min, and carrying out heat preservation reaction for 20-30 min;
(3.2) adding a polymerization catalyst into the mixture obtained in the step (3.1), and reacting for 15-20 min while maintaining the temperature at 75-85 ℃;
(3.3) heating to 88-92 ℃, and carrying out heat preservation reaction for 80-100 min; and cooling to 77-83 ℃, and then carrying out heat preservation reaction for 20-40 min to obtain the prepolymer of the reticular association type polyurethane composite modified organosilicon softener.
4. The preparation method of the reticular associative polyurethane composite modified silicone softener emulsion according to claim 1 or 2, wherein the step (4) is specifically:
(4.1) uniformly mixing the functional chain extender subjected to dehydration pretreatment in the step (2) with a cationic chain extender and 1/2 diluent for later use;
(4.2) adding 20% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organic silicon softening agent prepared in the step (3), and reacting for 50-70 min at 77-83 ℃;
(4.3) continuously adding 40% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3), reacting for 50-70 min at the temperature of 80-84 ℃, and adding 1/2 diluent to adjust the viscosity of a reaction system;
(4.4) continuously adding 40% of the mixture in the step (4.1) into the prepolymer of the reticular association type polyurethane composite modified organosilicon softening agent prepared in the step (3), and reacting for 50-70 min at the temperature of 80-84 ℃;
and (4.5) heating to 86-90 ℃, and reacting for 50-70 min to obtain the reticular association type polyurethane composite modified organosilicon softener polymer.
5. The preparation method of the reticular 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 ℃, adding a neutralizing agent, stirring and neutralizing for 20-30 min;
(5.2) adding an emulsifier and an organic silicon softening agent, fully mixing, and keeping stirring and neutralizing for 20-30 min;
(5.3) adding water, stirring at a high speed, emulsifying uniformly, and keeping stirring for 15-20 min;
and (5.4) standing and defoaming to prepare the reticular association type polyurethane composite modified organosilicon softener emulsion.
6. The preparation method of the reticular association type polyurethane composite modified organosilicon softener emulsion according to claim 1, wherein the amino silicone oil is amino silicone oil with an ammonia value of 0.3-0.6 and a solid content of 60-80%.
7. The method for preparing the reticular association type polyurethane composite modified organosilicon softener emulsion according to claim 1, wherein the water is soft water with the total hardness of less than 5 degrees.
8. The preparation method of the reticular associative polyurethane composite modified silicone softener emulsion according to claim 1, wherein the amount of the diluent is 72-78 wt% of the total weight of the polymerized monomers.
9. The preparation method of the reticular associative polyurethane composite modified silicone softener emulsion according to claim 1, wherein the using amount of the emulsifier is 9-14% of the weight of the amino silicone oil.
10. The reticular association type polyurethane composite modified organosilicon softener emulsion prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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