CN109629263B - Active-like adhesive composition and preparation method thereof - Google Patents
Active-like adhesive composition and preparation method thereof Download PDFInfo
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- CN109629263B CN109629263B CN201811585733.0A CN201811585733A CN109629263B CN 109629263 B CN109629263 B CN 109629263B CN 201811585733 A CN201811585733 A CN 201811585733A CN 109629263 B CN109629263 B CN 109629263B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5271—Polyesters; Polycarbonates; Alkyd resins
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67383—Inorganic compounds containing silicon
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an imitated active adhesive composition and a preparation method thereof. The novel imitated active adhesive comprises the following components: 0.5-10% by weight of inorganic nano powder, 15-35% by weight of clay, 2-15% by weight of alkyd resin, 15-45% by weight of silicon-acrylic copolymer and 25-40% by weight of water, based on the total weight of the novel imitated active adhesive. The composition has good stability and high self-thickening performance, does not contain formaldehyde agents, has the characteristics of obvious deepening effect, extremely high fastness, extremely soft hand feeling and the like when being applied to pure cotton fabrics, has the comprehensive effect equivalent to the performance of active printing (dyeing), and achieves the effect of imitating the active printing.
Description
Technical Field
The invention relates to an imitated active adhesive composition and a preparation method thereof. It is mainly suitable for the reactive printing process of cotton, hemp, viscose and blended fabrics thereof.
Background
The pigment printing is mainly characterized in that the pigment is fixed on the surface of the fiber by an adhesive film, and the pigment printing method has the advantages of simple printing process, energy conservation, no wastewater discharge, complete chromatogram, convenient color matching and sample imitation, clear printing outline, high certified product rate, reproducibility and the like.
However, pigment printing also has the disadvantages of poor crockfastness of printed fabrics, odor release in the operating environment, and the like. Although the novel coating and the matched novel auxiliary agent thereof are improved and developed without residue in various countries in the world for many years and great progress is obtained, the comprehensive balance in the aspects of hand feeling, fastness, penetration, environmental protection and the like is difficult. The key to solve the problems of hand feeling, color fastness, environmental protection and the like in pigment printing is mainly to synthesize the environment-friendly printing adhesive.
For example, CN 103524668A in publication discloses a preparation method of polyacrylate/nano ZnO composite pigment printing adhesive, which is a preparation method of pigment printing adhesive for fabrics, acrylate monomers, allyl glycidyl ether, nano ZnO and a double-bond-containing silane coupling agent are used as raw materials, the double-bond-containing silane coupling agent is used for chemically modifying nano ZnO, and the double-bond-containing silane coupling agent and the double-bond-containing monomer are polymerized by free radicals to prepare the polyacrylate/nano ZnO composite pigment printing adhesive.
Publication No. CN 104356960B discloses an inorganic high-temperature-resistant adhesive for aluminum alloy and a preparation method thereof. The adhesive is prepared from the following raw materials in percentage by weight: 35-45% of binder, 15-25% of attapulgite/nano silicon oxide composite powder, 5-10% of coupling agent, 3-6% of nano titanium oxide, 3-6% of dispersant, 1-3% of tackifier, 0.1-0.5% of defoaming agent and the balance of deionized water. Wherein the attapulgite/nano silicon oxide composite powder is a composite powder prepared by mixing attapulgite clay and nano silicon oxide powder according to the mass ratio of 100: 15-20. The adhesive has excellent high temperature resistance and acid and alkali resistance, uses inorganic materials as adhesive components, has the characteristics of high mechanical strength, strong bonding force, no pollution and the like, but is mainly applied to alloy materials and does not relate to textile application.
The publication No. CN 107338012A discloses a low-temperature environment-friendly imitated active adhesive, a preparation method thereof and application thereof, wherein the low-temperature environment-friendly imitated active adhesive comprises 35-38% of acrylic monomers by mass percent; 1-3% of nano silicon emulsion; 0.5 to 2 percent of cross-linking agent; 0.1 to 0.5 percent of water-soluble initiator; 0.2 to 0.5 percent of anionic emulsifier; 0.4-1% of nonionic emulsifier; deionized water and the balance. Although the invention has been described in detail for the preparation of the imitated active adhesive, the results of the low-temperature treatment are unclear, no specific data is provided for the low-temperature treatment effect, and the fastness difference of the low-temperature treatment effect is obvious compared with the fastness of the high-temperature (150 ℃) treatment from the fuzzy expression.
The researchers do a lot of work on the preparation of the adhesive, and the contradiction that the fastness and the hand feeling can not be simultaneously met exists all the time, so that the artificial active adhesive which is applied to the pure cotton fabric to ensure that the fastness is 4 grade or more and the hand feeling is 4-5 grade or more, has a self-thickening effect and has excellent application performance is difficult to synthesize.
Disclosure of Invention
One object of the present invention is to provide a simulated reactive adhesive composition comprising the following components:
the total weight of the novel reactive-imitation binder.
Another object of the present invention is to provide a method for preparing a novel reactive-imitation adhesive, which comprises:
adding the silicon-acrylic copolymer emulsion, clay and alkyd resin into a reaction kettle, uniformly stirring, then heating to 40-60 ℃, adding the inorganic nano powder, and uniformly stirring.
According to the invention, the high-viscosity double-end vinyl silicone oil and the acrylate and other comonomers are polymerized to synthesize the silicon-acrylic copolymer, so that the hand feeling of the copolymer is greatly improved; in the silicon-acrylic copolymer synthetic component, a special thickening monomer and an environment-friendly crosslinking monomer are copolymerized into a silicon-acrylic copolymer, so that the self-thickening performance of the polymer is greatly improved, the using amount of a thickening agent in an application process is obviously reduced, and the cost advantage is greatly improved; the clay is effectively combined with the silicon-propylene copolymer, so that the softness and the deepening performance of the silicon-propylene copolymer are greatly improved, and the clay and the silicon-propylene copolymer are integrated into a whole by utilizing the adsorption performance of the clay to form a stable clay-silicon-propylene copolymer compound, so that the stability of a product is ensured; by adding the alkyd resin and the inorganic nano powder, a nano layer is formed on the surface of the fiber and is uniformly combined with the high polymer resin, so that the strength and toughness of the resin film can be obviously improved, and the rubbing fastness is further improved.
The invention is a kind of good stability, high self-thickening property, the product is formaldehyde-free imitates the active binder, apply it to pure cotton fabric, it has effects of deepening apparently, the fastness is extremely high, the characteristic such as being extremely soft of hand feeling, the comprehensive effect is equivalent to the performance of the active printing (dyeing), has achieved the effect of imitating the active printing.
Detailed Description
In a preferred embodiment, the novel imitation active binder of the present invention comprises the following components:
the total weight of the novel reactive-imitation binder.
In a preferred embodiment, the inorganic nanopowder used is one or more of nano boride powder, nano oxide powder, and nano carbide powder, and the fineness of the nanopowder used is 10-100 nm, preferably 20-50 nm.
In a more preferred embodiment, the nano boride powder is one or a mixture of nano zirconium diboride powder and nano titanium diboride powder, the nano oxide powder is one or a mixture of nano titanium dioxide powder and nano zirconium dioxide powder, and the nano carbide powder is one or a mixture of nano silicon carbide powder, nano titanium carbide powder and nano zirconium carbide powder.
In a preferred embodiment, the clay used is one or a mixture of sodium bentonite and attapulgite. The average particle size of the clay is preferably 300-800nm, more preferably about 500 nm.
In a preferred embodiment, the alkyd resin used is a toluene diisocyanate-succinic acid synthetic modified alkyd resin having a viscosity of 4000-6000mPa · s and a hydroxyl value (mgKOH/g) of 110-130, preferably about 125.
In a more preferred embodiment, the silicon-acrylic copolymer is prepared by emulsion polymerization of silicon monomer, soft monomer, hard monomer, crosslinking monomer, functional monomer and thickening monomer through a reactive emulsifier, and the weight average molecular weight of the silicon-acrylic copolymer is 1-8 x 104Preferably 2-6X 104。
In a particularly preferred embodiment, the silicon monomer used is a bis-terminal-vinyl-polysiloxane, the soft monomer used is n-butyl acrylate, the hard monomer used is one or a mixture of dimethylaminoethyl methacrylate, vinyl acetate, methyl methacrylate, acrylonitrile and vinyl versatate, the functional monomer used is acrylic acid or methacrylic acid, and the thickening monomer used is C12-20One or two of long-chain alkyl alcohol polyoxyethylene ether methacrylate (BEM, Rodiya company) or tristyrylphenol polyoxyethylene ether methacrylate (SEM-25, Rodiya company), and the crosslinking monomer is one or more of tetraethylene glycol dimethacrylate, acetoacetoxy ethyl methacrylate, hexamethylenediamine and adipic dihydrazide.
In a particularly preferred embodiment, the bisvinylpolysiloxanes used have a viscosity of from 15 to 30 ten thousand mPas (25 ℃).
In a particularly preferred embodiment, in the emulsion polymerization of the silicon-propylene copolymer, the reactive emulsifier used is an allyl polyoxyethylene ether or salt (EO ═ 25 to 35), such as a mixture of allyl polyoxyethylene ether sulfate (EO ═ 30) and allyl polyoxyethylene ether (EO ═ 30). In the emulsion polymerization of the silicon-propylene copolymer, a peroxide is used as a radical initiator.
In a particularly preferred embodiment, the weight ratio of the silicon monomer, soft monomer, hard monomer, functional monomer, crosslinking monomer, thickening monomer and reactive emulsifier used to form the silicon-acrylic copolymer is 5-25:35-65:5-15:1-5:1-5:5-15:5-10, preferably 10-22:40-60:5-15:2-4:2-4:5-12: 5-10.
In a more preferred embodiment, there is also provided a method of making a novel imitation reactive adhesive comprising: the preparation method comprises the steps of sequentially adding the emulsion of the silicon-acrylic copolymer, clay and alkyd resin into a reaction kettle, uniformly stirring at a high rotating speed, heating to 40-60 ℃, adding inorganic nano powder, and continuously uniformly stirring after the addition.
Compared with the prior art, the invention has the following advantages and effects: the inorganic material and the organic polymer are effectively combined, firstly, the silicon-acrylic copolymer emulsion which has better stability, higher self-thickening performance and no formaldehyde is prepared, then the silicon-acrylic copolymer emulsion is compounded with a plurality of components and applied to the pure cotton fabric, and the silicon-acrylic copolymer emulsion has obvious deepening effect, extremely high friction fastness, extremely soft hand feeling, equivalent comprehensive effect to the performance of active printing (dyeing), and the effect of imitating the active printing is achieved.
Examples
The performance of the novel imitation reactive binder of the invention in the paint printing process is verified by the following tests.
Pigment printing and reactive printing test
1. Fabric: pure cotton knitted fabric
2. Pigment printing color paste formula
| Raw materials | Ratio (%) |
| Thickener 5228 for pigment printing | 1-2 |
| Paint brilliant blue 8302 | 3 |
| Adhesive agent | 15 |
| Water (W) | Y |
| Total up to | 100 |
3. Paint printing process
Pigment printing → baking (150 ℃, 3 minutes)
4. Formula of active printing color paste
5. The reactive printing process comprises the following steps:
printing → drying → steaming (105 ℃ C.. times.8 min) → cold water washing → warm water washing (80 ℃ C.) → soaping (95 ℃ C., SW conc., 2g/L) → warm water washing → cold water washing → drying.
6. Performance testing
6.1 apparent printing depth (K/S value)
The apparent color yield of the printed fabric was tested using a Datacolor 400 color meter. A larger K/S value indicates a higher apparent color yield.
6.2 stability
And (3) placing the product in a closed sample bottle, placing for 6 months at 25 ℃, and observing whether the product is layered or not and whether a gel substance appears or not.
6.3 gel fraction
After the polymerization reaction is finished, collecting all reaction gels, washing and drying at 105 ℃ to constant weight, and calculating the gel rate according to the formula (1):
gel fraction (gel weight/total monomer weight) × 100% (1)
6.4 glass transition temperature (Tg)
And uniformly dispersing the adhesive emulsion on a dry and clean polytetrafluoroethylene plate, naturally drying, and after film formation, putting the adhesive film into a 60 ℃ oven for drying for 6 days to obtain a film with the thickness of about 1 mm. The glass transition temperature is measured by a Q2000 type differential scanning calorimetry analyzer, the temperature rising speed is 10 ℃/min, and the temperature range is-50 ℃ to 50 ℃.
6.5 measurement of viscosity
Spindle # 6 was selected for testing at 25 ℃ using Brookfield RVDV-II + Pro using a Brookfield viscometer.
6.6 Formaldehyde content test
The determination is carried out according to GB/T5543-2006 determination of total formaldehyde content, free formaldehyde content and hydroxymethyl formaldehyde content of the resin finishing agent.
6.7 rubbing fastness
Dry and wet rub fastness: according to GB/T3920-.
6.8 hand feeling
And (4) performing a hand touch method. Softness was rated best on 5 grades and worst on 1 grade by a panel of 5 people touching the printed fabric individually. The average number of 5 persons is the evaluation result.
6.9 weight average molecular weight determination: measured by HLC-8320GPC type gel permeation chromatography (Nippon Tosoh Co., Ltd.) with DMF as the mobile phase at 25 ℃ and polymethyl methacrylate (PMMA) as the reference.
Example 1:
the formula adopted in the embodiment comprises the following raw materials:
the invention also provides a preparation method of the novel imitated active adhesive, which comprises the following steps: the method comprises the following steps:
(1) the preparation method of the silicon-propylene copolymer emulsion 1 comprises the following steps:
the silicon-propylene copolymer emulsion 1 comprises the following components:
the preparation method of the silicon-propylene copolymer emulsion 1 comprises the following steps:
firstly, 1 part by weight of allyl polyoxyethylene ether sulfate (EO 30, NRS-1230, purchased from Shanghai loyalty chemical Co., Ltd.), 2 parts by weight of allyl polyoxyethylene ether (EO 30, AE-330, purchased from Shanghai loyalty chemical Co., Ltd.) and 30 parts by weight of deionized water are mixed, the temperature is raised to 50 ℃, 80r/min is stirred for 20min, and 33 parts by weight of emulsifier solution is prepared;
dropwise adding 5 parts by weight of double-end vinyl polysiloxane (with the viscosity of 15 ten thousand mPa & s, at 25 ℃), 3 parts by weight of dimethylaminoethyl methacrylate, 2 parts by weight of acrylonitrile, 25 parts by weight of n-butyl acrylate, 1 part by weight of acrylic acid, 3 parts by weight of BEM and 0.5 part by weight of acetoacetoxy ethyl methacrylate into an emulsifier solution in sequence, stirring at the speed of 100r/min, the dropwise adding temperature of 55 ℃, and the dropwise adding time of 1h, and continuing to emulsify for 1h after completing dropwise adding to prepare 72.5 parts by weight of pre-emulsion;
mixing 18 parts by weight of deionized water and 20 parts by weight of pre-emulsion, heating to 80 ℃, dropwise adding 2 parts by weight of 10% ammonium persulfate solution, reacting for 20min, then continuously and respectively dropwise adding the rest of pre-emulsion and 3 parts by weight of 10% ammonium persulfate solution, completing dropwise adding after 3h, reacting for 2h at 85 ℃, cooling to 60 ℃, adding 0.5 part by weight of hexamethylenediamine, stirring for 10min, continuously cooling to 45 ℃, adding 5 parts by weight of 12% sodium hydroxide solution, neutralizing to 6-8, and preparing 100 parts by weight of silicon-propylene copolymer emulsion 1, wherein the weight-average molecular weight is 2 multiplied by 104The solid content was about 43.1%.
(2) The preparation method of the imitated active adhesive comprises the following steps: and (2) sequentially adding 65 parts by weight of the silicon-propylene copolymer emulsion 1 prepared in the step (1), 20 parts by weight of sodium bentonite and 10 parts by weight of alkyd resin (HKP-3180, purchased from Shandong Jiaying chemical Co., Ltd.) into a reaction kettle, stirring for 2 hours at the rotating speed of 1000r/min, then heating to 50 ℃, adding 5 parts by weight of nano titanium diboride powder, and continuing stirring for 1 hour after the addition is finished, thus obtaining the nano titanium diboride composite material.
Example 2:
the invention also provides a preparation method of the novel imitated active adhesive, which comprises the following steps: the method comprises the following steps:
(1) the preparation method of the silicon-propylene copolymer emulsion 2 comprises the following steps:
the silicon-propylene copolymer emulsion 2 comprises the following components:
the preparation method of the silicon-propylene copolymer emulsion 2 comprises the following steps: firstly, 1 part by weight of allyl polyoxyethylene ether sulfate (EO 30, NRS-1230, purchased from Shanghai loyalty chemical Co., Ltd.), 3 parts by weight of allyl polyoxyethylene ether (EO 30, AE-330, purchased from Shanghai loyalty chemical Co., Ltd.) and 30 parts by weight of deionized water are mixed, the temperature is raised to 60 ℃, 80r/min is stirred for 20min, and 34 parts by weight of emulsifier solution is prepared;
sequentially dropwise adding 7 parts by weight of double-end vinyl polysiloxane (with the viscosity of 20 ten thousand mPa & s, at the temperature of 25 ℃), 2 parts by weight of acrylonitrile, 1 part by weight of vinyl versatate (Veova 9), 24 parts by weight of n-butyl acrylate, 1 part by weight of acrylic acid, 4 parts by weight of SEM-25 and 1 part by weight of acetoacetoxy ethyl methacrylate into an emulsifier solution, stirring at the speed of 100r/min, at the dropwise adding temperature of 60 ℃, continuing to emulsify for 1h after completing dropwise adding, and preparing 74 parts by weight of pre-emulsion;
mixing 15.2 parts by weight of deionized water and 20 parts by weight of pre-emulsion, heating to 80 ℃, dropwise adding 1 part by weight of 10% ammonium persulfate solution, reacting for 20min, and continuously dropwise adding the rest of pre-emulsion and 4 parts by weight of 10%Dropping ammonium persulfate solution with concentration for 4h, reacting at 85 deg.C for 2h, cooling to 60 deg.C, adding 0.5 weight part of adipic dihydrazide, stirring for 10min, further cooling to 45 deg.C, adding 5 weight parts of 12% sodium hydroxide solution, and neutralizing to 6-8 to obtain 100 weight parts of silicon-propylene copolymer emulsion 2 with weight average molecular weight of 3 × 104The solid content was about 45.6%.
(2) The preparation method of the novel imitated active adhesive comprises the following steps: and (2) sequentially adding 62 parts by weight of the silicon-propylene copolymer emulsion prepared in the step (1), 30 parts by weight of attapulgite and 5 parts by weight of alkyd resin (HKP-3180, purchased from Kagaku chemical Co., Ltd., Shandong) into a reaction kettle, stirring for 2 hours at the rotating speed of 1000r/min, heating to 60 ℃, adding 1.5 parts by weight of nano zirconium dioxide powder and 1.5 parts by weight of nano zirconium diboride powder, and continuing stirring for 1 hour after the addition is finished, thus obtaining the silicon-propylene copolymer emulsion.
Example 3:
the invention also provides a preparation method of the novel imitated active adhesive, which comprises the following steps: the method comprises the following steps:
(1) the preparation method of the silicon-propylene copolymer emulsion 3 comprises the following steps:
the silicon-propylene copolymer emulsion 3 comprises the following components:
the preparation method of the silicon-propylene copolymer emulsion 3 comprises the following steps: firstly, 1 part by weight of allyl polyoxyethylene ether sulfate (EO 30, NRS-1230, purchased from Shanghai loyalty chemical Co., Ltd.), 3 parts by weight of allyl polyoxyethylene ether (EO 30, AE-330, purchased from Shanghai loyalty chemical Co., Ltd.) and 30 parts by weight of deionized water are mixed, the temperature is raised to 55 ℃, 80r/min is stirred for 20min, and 34 parts by weight of emulsifier solution is prepared;
dripping 10 parts by weight of double-end vinyl polysiloxane (with the viscosity of 25 ten thousand mPa & s, at the temperature of 25 ℃), 2 parts by weight of vinyl acetate, 3 parts by weight of acrylonitrile, 20 parts by weight of n-butyl acrylate, 1 part by weight of methacrylic acid, 5 parts by weight of SEM-25 and 1 part by weight of tetraethylene glycol dimethacrylate into an emulsifier solution in sequence, stirring at the speed of 80r/min, at the dripping temperature of 50 ℃, for 1h, and continuing to emulsify for 1h after finishing dripping to prepare 76 parts by weight of pre-emulsion;
mixing 13.5 parts by weight of deionized water and 20 parts by weight of pre-emulsion, heating to 80 ℃, dropwise adding 2 parts by weight of 10% ammonium persulfate solution, reacting for 20min, continuously dropwise adding the rest 80% pre-emulsion and 3 parts by weight of 10% ammonium persulfate solution, reacting for 3h, reacting for 2h at 85 ℃, cooling to 60 ℃, adding 0.5 part by weight of hexamethylenediamine, stirring for 10min, continuously cooling to 50 ℃, adding 5 parts by weight of 12% sodium hydroxide solution, and neutralizing to 6-8 to obtain 100 parts by weight of nuclear polymer particle emulsion 3, wherein the weight-average molecular weight is 4 multiplied by 10, and the weight-average molecular weight is 4 multiplied by 104The content was about 47.6%.
(2) The preparation method of the novel imitated active adhesive comprises the following steps: and (2) sequentially adding 60 parts by weight of the silicon-propylene copolymer emulsion 3 prepared in the step (1), 25 parts by weight of sodium bentonite and 10 parts by weight of alkyd resin (HKP-3180, purchased from Shandong Jiaying chemical Co., Ltd.) into a reaction kettle, stirring for 2 hours at the rotating speed of 1000r/min, heating to 50 ℃, adding 2 parts by weight of nano silicon carbide powder, 2 parts by weight of nano titanium carbide powder and 1 part by weight of nano zirconium carbide powder, and continuously stirring for 1 hour after the addition is finished, thus obtaining the silicon-propylene copolymer emulsion.
Example 4:
the invention also provides a preparation method of the novel imitated active adhesive, which comprises the following steps: the method comprises the following steps:
(1) the preparation method of the silicon-propylene copolymer emulsion 4 comprises the following steps:
the silicone-acrylic copolymer emulsion 4 comprises the following components:
the preparation method of the silicon-propylene copolymer emulsion 4 comprises the following steps: firstly, 1 part by weight of allyl polyoxyethylene ether sulfate (EO 30, NRS-1230, purchased from Shanghai loyalty chemical Co., Ltd.), 2 parts by weight of allyl polyoxyethylene ether (EO 30, AE-330, purchased from Shanghai loyalty chemical Co., Ltd.) and 30 parts by weight of deionized water are mixed, the temperature is raised to 50 ℃, 80r/min is stirred for 20min, and 33 parts by weight of emulsifier solution is prepared;
dropwise adding 5 parts by weight of double-end vinyl polysiloxane (with the viscosity of 30 ten thousand mPa & s, at the temperature of 25 ℃), 2 parts by weight of methyl methacrylate, 2 parts by weight of acrylonitrile, 28 parts by weight of n-butyl acrylate, 1.5 parts by weight of methacrylic acid, 4 parts by weight of BEM and 1 part by weight of acetoacetoxy ethyl methacrylate into an emulsifier solution in sequence, stirring at the speed of 80r/min, at the dropwise adding temperature of 50 ℃, continuously emulsifying for 1h after dropwise adding is finished, and preparing 76.5 parts by weight of pre-emulsion;
mixing 14.3 parts by weight of deionized water and 20 parts by weight of pre-emulsion, heating to 80 ℃, dropwise adding 1 part by weight of ammonium persulfate solution with the concentration of 10%, reacting for 20min, continuously dropwise adding the rest 80% of pre-emulsion and 2 parts by weight of ammonium persulfate solution with the concentration of 10%, completing dropwise adding for 3h, reacting for 2h at 85 ℃, cooling to 60 ℃, adding 0.5 part by weight of hexamethylenediamine, stirring for 10min, continuously cooling to 50 ℃, adding 5.7 parts by weight of sodium hydroxide solution with the concentration of 12%, neutralizing to 6-8, and preparing 100 parts by weight of nuclear polymer particle emulsion 4, wherein the weight average molecular weight is 6 multiplied by 10, and the weight average molecular weight is 6 multiplied by 104The solid content was about 48%.
(2) The preparation method of the novel imitated active adhesive comprises the following steps: and (2) sequentially adding 60 parts by weight of the silicon-propylene copolymer emulsion 4 prepared in the step (1), 25 parts by weight of sodium bentonite and 10 parts by weight of alkyd resin (HKP-3180, purchased from Shandong Jiaying chemical Co., Ltd.) into a reaction kettle, stirring for 2 hours at the rotating speed of 1000r/min, heating to 50 ℃, adding 3 parts by weight of nano titanium carbide powder and 2 parts by weight of nano zirconium carbide powder, and continuing stirring for 1 hour after the addition is finished, thus obtaining the nano titanium carbide powder.
The inventive examples 1-4 were tested for stability, gel fraction, glass transition temperature, and formaldehyde content of the product according to the inventive test methods, and the results are shown in Table 1.
Table 1 examples 1-6 properties of adhesives prepared
As shown in Table 1, the stability of examples 1 to 4 is good, the glass transition temperature is-30 ℃ or below, and the product is formaldehyde-free and belongs to a green and environment-friendly product.
In order to better embody the effect of the invention, the pure cotton knitted fabric is pigment printed by using the adhesive A (a commercial imitated active adhesive) and the adhesive B (a commercial non-imitated active adhesive) and the invention, and the results are compared with the performance of the active printed fabric, and the results are shown in Table 2.
Table 2 examples 1-4 compare the results of commercial adhesive A, B and reactive brilliant blue printed fabrics
As can be seen from Table 2, examples 1-4 have a lower amount of thickener 5228 compared to binders A and B, while printing depth, crockfastness and hand feel are significantly better than binders A and B, and the specific structure and specific components of the present invention allow for significantly lower thickener usage and significantly lower overall printing cost relative to commercially available binders A and B. Compared with the effect of the reactive brilliant blue printed fabric, the K/S value, dry friction, wet friction and hand feeling indexes of the pure cotton knitted fabric are the same, which shows that the indexes of fastness, hand feeling and the like of the reactive brilliant blue printed fabric achieve the reactive printing effect.
Although the present invention has been described with reference to the above embodiments, it should be understood that the scope of the present invention is not limited thereto, and that various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the present invention.
Claims (6)
1. A simulated active adhesive composition for simulating active printing of pure cotton fabric comprises the following components:
wherein the inorganic nano powder is one or a mixture of several of nano boride powder, nano oxide powder and nano carbide powder, and the fineness of the nano powder is 20-50 nm;
the silicon-propylene copolymer is prepared by emulsion polymerization of a silicon monomer, a soft monomer, a hard monomer, a functional monomer, a crosslinking monomer, a thickening monomer and a reactive emulsifier, wherein the silicon monomer is double-ended vinyl polysiloxane, the viscosity of the double-ended vinyl polysiloxane at 25 ℃ is 15-30 ten thousand mPa.s,
wherein the weight ratio of the silicon monomer, the soft monomer, the hard monomer, the functional monomer, the crosslinking monomer, the thickening monomer and the reactive emulsifier for forming the silicon-acrylic copolymer is 5-25:35-65:5-15:2-4:2-4:5-12: 5-10; the soft monomer is n-butyl acrylate, the hard monomer is one or more of dimethylaminoethyl methacrylate, vinyl acetate, methyl methacrylate, acrylonitrile and vinyl versatate, the functional monomer is acrylic acid or methacrylic acid, and the thickening monomer is C12-20One or two of long-chain alkyl alcohol polyoxyethylene ether methacrylate or tristyrylphenol polyoxyethylene ether methacrylate, wherein the crosslinking monomer is one or a mixture of more of tetraethylene glycol dimethacrylate, acetoacetoxy ethyl methacrylate, hexamethylenediamine and adipic dihydrazide; the reactive emulsifier is allyl polyoxyethylene ether or salt with EO of 25-35.
2. The simulated reactive adhesive composition of claim 1, wherein: the nano boride powder is one or a mixture of nano zirconium diboride powder and nano titanium diboride powder, the nano oxide powder is one or a mixture of nano titanium oxide powder and nano zirconium oxide powder, and the nano carbide powder is one or a mixture of nano silicon carbide powder, nano titanium carbide powder and nano zirconium carbide powder.
3. The simulated reactive adhesive composition of claim 1, wherein: the clay is one or two of sodium bentonite and attapulgite, and the average particle size of the clay is 300-800 nm.
4. The simulated reactive adhesive composition of claim 1, wherein: the alkyd resin is synthesized and modified by toluene diisocyanate-succinic acid, the viscosity measured at 25 ℃ is 4000-6000 mPa.s, and the hydroxyl value is 110-130 mgKOH/g.
5. The simulated reactive adhesive composition of claim 1, wherein: the silicon-propylene copolymer has a weight average molecular weight of 1-8 × 104。
6. The method of making the simulated reactive adhesive composition of claim 1 comprising:
adding the silicon-acrylic copolymer emulsion, clay and alkyd resin into a reaction kettle, uniformly stirring, then heating to 40-60 ℃, adding the inorganic nano powder, and uniformly stirring.
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